TWI420006B - Crystallographically oriented tantalum pentoxide and methods of making same - Google Patents

Crystallographically oriented tantalum pentoxide and methods of making same Download PDF

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TWI420006B
TWI420006B TW098117829A TW98117829A TWI420006B TW I420006 B TWI420006 B TW I420006B TW 098117829 A TW098117829 A TW 098117829A TW 98117829 A TW98117829 A TW 98117829A TW I420006 B TWI420006 B TW I420006B
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crystalline
hydrogen
pentoxide
antimony pentoxide
ruthenium
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TW201002878A (en
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Vishwanath Bhat
Vassil Antonov
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Micron Technology Inc
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Description

結晶取向之五氧化二鉭及其製造方法Crystal orientation of antimony pentoxide and its production method

積體電路器件之按比例縮小已產生將高介電常數(亦即，高介電係數)材料併入至電容器及閘極之需要。對新的高介電常數材料及製程之探求正變得愈加重要，因為當前技術之最小大小實際上受到標準介電材料之使用的約束。The scaling down of integrated circuit devices has created the need to incorporate high dielectric constant (i.e., high dielectric constant) materials into capacitors and gates. The search for new high dielectric constant materials and processes is becoming increasingly important as the minimum size of current technology is actually constrained by the use of standard dielectric materials.

五氧化二鉭(例如，Ta2 O5 )由於其高介電常數(例如，30)及低漏電流而作為用於諸如DRAM電容器之應用的高介電係數材料已引起注意。更進一步的注意已指向用於此等應用之結晶五氧化二鉭，因為結晶五氧化二鉭之薄膜具有為60之介電常數，其約為非晶五氧化二鉭之薄膜的介電常數之兩倍。然而，一些高介電常數材料具有可加以改良之其他特性，此可導致材料及併有此等材料之物品的改良之效能。Bismuth pentoxide (e.g., Ta 2 O 5 ) has attracted attention as a high-k material for applications such as DRAM capacitors due to its high dielectric constant (e.g., 30) and low leakage current. Further attention has been directed to crystalline bismuth pentoxide for such applications because the crystalline pentoxide film has a dielectric constant of 60 which is about the dielectric constant of the amorphous pentoxide film. double. However, some high dielectric constant materials have other properties that can be modified, which can result in improved performance of materials and articles having such materials.

正在尋求製備用於當前及新一代器件(例如，積體電路器件)的高介電常數材料及具有高介電常數材料之新物品之新方法。New methods for preparing high dielectric constant materials and new articles with high dielectric constant materials for current and next generation devices (eg, integrated circuit devices) are being sought.

多晶材料通常含有複數個由晶界分隔之個別晶體或晶粒。此等晶粒保留晶體之特徵性結構，但可藉由其主軸之相對旋轉而相對於相鄰晶體(例如，晶粒)不同地取向。多晶材料中之晶界可負面地影響(例如)材料之物理及電特性。當晶界對準時，一些特性可能更進一步受到負面影響。雖然一些結晶(例如，多晶)介電材料展現出高介電常數，但在此等材料中之晶界對準可負面地影響介電材料及併有該材料之器件的效能。舉例而言，介電材料中之晶界對準可導致增加的晶界誘發之洩漏，其中電流可漏過經受所施加電場的絕緣介電材料。因此，晶界對準之減少，且因此結晶高介電常數材料中的晶界誘發之洩漏之減少可提供新的物品、構造及器件。舉例而言，此等物品、構造及器件可用於消費者產品應用、電子應用、半導體器件應用、電容器應用及其他應用中。Polycrystalline materials typically contain a plurality of individual crystals or grains separated by grain boundaries. These grains retain the characteristic structure of the crystal, but can be oriented differently relative to adjacent crystals (e.g., grains) by relative rotation of their major axes. The grain boundaries in the polycrystalline material can negatively affect, for example, the physical and electrical properties of the material. When the grain boundaries are aligned, some characteristics may be further adversely affected. While some crystalline (eg, polycrystalline) dielectric materials exhibit high dielectric constants, grain boundary alignment in such materials can negatively impact the performance of dielectric materials and devices having such materials. For example, grain boundary alignment in a dielectric material can result in increased grain boundary induced leakage, where current can leak through the insulating dielectric material that is subject to the applied electric field. Thus, the reduction in grain boundary alignment, and thus the reduction in grain boundary induced leakage in crystalline high dielectric constant materials, can provide new articles, configurations, and devices. For example, such articles, structures, and devices can be used in consumer product applications, electronic applications, semiconductor device applications, capacitor applications, and other applications.

本文中提供形成氧化物(例如，Ta2 O5 )之方法。本文中亦提供包括具有不同結晶取向之五氧化二鉭之物品及器件。Provided herein to form an oxide (e.g., Ta 2 O 5) of the method. Articles and devices comprising tantalum pentoxide having different crystal orientations are also provided herein.

本揭示案之一態樣為形成氧化物之方法。該方法包括使含釕材料與包括含鉭前驅物之第一蒸汽接觸。該方法進一步包括提供包括一或多個入口流及一出口流之水蒸汽產生器。該出口流包括(例如)水及視情況氫分子(H2 )。該方法進一步包括使該含釕材料與該出口流在對於於其上形成結晶五氧化二鉭有效之條件下接觸。於本文中使用時，「一」、「該」與「至少一」可互換使用，且意謂一個或一個以上。One aspect of the present disclosure is a method of forming an oxide. The method includes contacting a ruthenium containing material with a first vapor comprising a ruthenium containing precursor. The method further includes providing a water vapor generator comprising one or more inlet streams and an outlet stream. The outlet stream includes, for example, water and optionally hydrogen molecules (H 2 ). The method further includes contacting the rhodium-containing material with the outlet stream under conditions effective to form crystalline antimony pentoxide thereon. As used herein, "a", "an" and "said" are used interchangeably and mean one or more.

在一些實施例中，水蒸汽產生器(WVG)將催化劑用於使包括氫分子(H2 )及氧分子(O2 )之一或多個入口流反應以產生包括水蒸汽之出口流。該一或多個入口流可包括(例如)含氫入口流及含氧入口流。在一些實施例中，含氫入口流可包括(例如)氫分子(H2 )、氫原子(H)、合成氣體(N2 /H2 )、氨(NH3 )、烴(例如，CH4 )、醇(例如，CH3 OH)，或其組合。在一些實施例中，含氧入口流可包括(例如)氧分子(O2 )、氧原子(O)、臭氧(O3 )、氧化亞氮(N2 O)、氧化氮(NO)、二氧化氮(NO2 )、五氧化二氮(N2 O5 )、過氧化氫(H2 O2 )，或其組合。在一或多個實施例中，含氫入口流及含氧入口流分別包括氫分子(H2 )及氧分子(O2 )。用於水蒸汽產生器系統之催化劑可包括金屬，諸如，鈀、鉑、鎳、鐵、鉻、釕、銠；其合金；或其組合。水蒸汽產生器描述於(例如)國際申請公開案第WO 2005/113852號(Myo等人)及第WO 2005/117087號(Narwankar等人)中。在來自Ultra Clean Technology(Menlo Park，CA)之商標名稱CATALYTIC STEAM GENERATION SYSTEM及來自Fujikin of America,Inc.(Santa Clara，CA)之商標名稱WATER VAPOR GENERATOR下，可獲得水蒸汽產生器。In some embodiments, the steam generator (the WVG) comprises a catalyst for molecular hydrogen (H 2) and oxygen molecules (O 2) one or more inlet flow comprising reacted to produce an outlet stream of water vapor. The one or more inlet streams can include, for example, a hydrogen-containing inlet stream and an oxygen-containing inlet stream. In some embodiments, the hydrogen-containing inlet stream can include, for example, hydrogen molecules (H 2 ), hydrogen atoms (H), synthesis gas (N 2 /H 2 ), ammonia (NH 3 ), hydrocarbons (eg, CH 4 ) ), an alcohol (eg, CH 3 OH), or a combination thereof. In some embodiments, the oxygen-containing inlet stream can include, for example, oxygen molecules (O 2 ), oxygen atoms (O), ozone (O 3 ), nitrous oxide (N 2 O), nitrogen oxides (NO), Nitric oxide (NO 2 ), dinitrogen pentoxide (N 2 O 5 ), hydrogen peroxide (H 2 O 2 ), or a combination thereof. In one or more embodiments, the hydrogen-containing inlet stream and the oxygen-containing inlet stream comprise hydrogen molecules (H 2 ) and oxygen molecules (O 2 ), respectively. Catalysts for use in the steam generator system can include metals such as palladium, platinum, nickel, iron, chromium, ruthenium, iridium; alloys thereof; or combinations thereof. The water vapor generator is described, for example, in International Application Publication No. WO 2005/113852 (Myo et al.) and WO 2005/117087 (Narwankar et al.). A water vapor generator is available under the trade name CATALYTIC STEAM GENERATION SYSTEM from Ultra Clean Technology (Menlo Park, CA) and the trade name WATER VAPOR GENERATOR from Fujikin of America, Inc. (Santa Clara, CA).

含氫入口流及含氧入口流可各自藉由(例如)質量流量控制器來相互獨立地控制。因此，當按2：1之氫對氧原子比將氫及氧引入至水蒸汽產生器時，水蒸汽產生器出口蒸汽為水蒸汽，相對於熱解蒸氣系統，其通常具有超高純度及減少的污染。蒸氣之非吾人所樂見之污染可導致對基板表面之污染。若氫對氧比率不同於2：1比率，則在水蒸汽產生器出口蒸汽中可能存在過剩的氧或過剩的氫。於本文中使用時，通常在包括「及/或」之意義上使用術語「或」，除非使用之上下文另有清楚指示。The hydrogen-containing inlet stream and the oxygen-containing inlet stream can each be controlled independently of each other by, for example, a mass flow controller. Thus, when a hydrogen to oxygen ratio of 2:1 is introduced to the steam generator, the steam generator outlet steam is water vapor, which typically has ultra high purity and reduced relative to the pyrolysis vapor system. Pollution. Contamination of vapors that are not desired by us can cause contamination of the surface of the substrate. If the hydrogen to oxygen ratio is different from the 2:1 ratio, there may be excess oxygen or excess hydrogen in the steam generator outlet steam. The term "or" is used in the sense of "and/or" unless the context of use is otherwise clearly indicated.

控制至水蒸汽產生器的一或多個入口流中之氫對氧比率之能力可用於本揭示案之一些實施例中。在一些實施例中，修改水蒸汽產生器之一或多個入口流的氫對氧比率可允許具有特定結晶取向的材料之選擇性形成(例如，沈積)。在一些實施例中，在沈積期間修改氫對氧比率可允許以特定結晶取向沈積給定材料(例如，五氧化二鉭)，繼之以不同結晶取向沈積相同材料。以此方式，影響組合材料(例如，介電材料或層)之晶界對準且藉此減少材料之晶界誘發之洩漏可為可能的。The ability to control the ratio of hydrogen to oxygen in one or more inlet streams to the steam generator can be used in some embodiments of the present disclosure. In some embodiments, modifying the hydrogen to oxygen ratio of one or more inlet streams of the water vapor generator may allow for selective formation (eg, deposition) of materials having a particular crystalline orientation. In some embodiments, modifying the hydrogen to oxygen ratio during deposition may allow deposition of a given material (eg, tantalum pentoxide) in a particular crystalline orientation, followed by deposition of the same material in different crystalline orientations. In this way, it may be possible to influence the grain boundary alignment of the composite material (eg, a dielectric material or layer) and thereby reduce the grain boundary induced leakage of the material.

可以許多方式來實現控制水蒸汽產生器之一或多個入口流的氫對氧比率。舉例而言，可藉由在氫及氧源中之每一者上使用獨立的流速控制器來控制氫對氧比率。視可用之氫及氧源及所使用之裝置而定，控制氫對氧比率之其他方法對一般熟習此項技術者而言將顯而易見。The hydrogen to oxygen ratio of one or more inlet streams of the steam generator can be controlled in a number of ways. For example, the hydrogen to oxygen ratio can be controlled by using a separate flow rate controller on each of the hydrogen and oxygen sources. Other methods of controlling the hydrogen to oxygen ratio will be apparent to those of ordinary skill in the art, depending upon the source of hydrogen and oxygen available and the equipment used.

如與在一些實施例中的水安瓿之使用相比，水蒸汽產生器之使用可提供在氣相沈積製程中之額外的操作自由度。水安瓿按氫對氧之恆定且不可變之原子比使水汽化。控制至水蒸汽產生器的氫與氧之流速允許在水蒸汽產生器出口蒸汽中的氫對氧之可變原子比，除了水之外，水蒸汽產生器出口蒸汽可視情況含有過剩的氫或過剩的氧。The use of a water vapor generator can provide additional operational freedom in a vapor deposition process as compared to the use of water ampoules in some embodiments. Water ampoules vaporize water at a constant and immutable atomic ratio of hydrogen to oxygen. The flow rate of hydrogen to oxygen controlled to the steam generator allows for a variable atomic ratio of hydrogen to oxygen in the steam at the outlet of the steam generator. In addition to water, the steam outlet steam may optionally contain excess hydrogen or excess Oxygen.

水蒸汽產生器可准許一或多個入口流的氫與氧之非化學計量比(例如，氫對氧原子比不等於二)，但歸因於操作安全考慮，亦可具有對氫對氧比率之限制。在本揭示案中之一或多個實施例中，水蒸汽產生器之一或多個入口流之氫對氧原子比可為至少6：3。另外，水蒸汽產生器之一或多個入口流之氫對氧原子比可為至多8：3。可使用至少6：3且至多8：3之任何氫對氧原子比(例如，基於原子，每3份氧，6.1、6.2、6.4、6.67、6.8、6.9、7.0、7.1、7.2、7.33、7.4、7.6、7.8或7.9份氫)。於本文中使用時，藉由端點之數字範圍的列舉包括在彼範圍內包含的所有數(例如，1至5包括1、1.5、2、2.75、3、3.80、4、5等)。通常，水蒸汽產生器之一或多個入口流及出口流之氫對氧原子比實質上相同。The water vapor generator may permit a non-stoichiometric ratio of hydrogen to oxygen in one or more inlet streams (eg, hydrogen to oxygen atomic ratio is not equal to two), but may also have a hydrogen to oxygen ratio due to operational safety considerations. The limit. In one or more embodiments of the present disclosure, one or more inlet streams of the water vapor generator may have a hydrogen to oxygen atom ratio of at least 6:3. Additionally, one or more inlet streams of the steam generator may have a hydrogen to oxygen atom ratio of up to 8:3. Any hydrogen to oxygen atom ratio of at least 6:3 and up to 8:3 can be used (eg, based on atoms, every 3 parts of oxygen, 6.1, 6.2, 6.4, 6.67, 6.8, 6.9, 7.0, 7.1, 7.2, 7.33, 7.4) , 7.6, 7.8 or 7.9 parts of hydrogen). As used herein, the enumeration of numerical ranges by endpoints includes all numbers that are included in the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> <RTIgt; Typically, the hydrogen to oxygen atom ratio of one or more of the inlet and outlet streams of the water vapor generator is substantially the same.

根據本揭示案的形成氧化物之方法可包括使含釕材料與包括含鉭前驅物之蒸汽接觸。該方法可進一步包括提供包括一或多個入口流及一出口流之水蒸汽產生器，其中該一或多個入口流包括氫及氧，且其中該一或多個入口流中之氫對氧比率可控制。該方法可更進一步包括使該含釕材料與該出口流在對於於其上形成結晶五氧化二鉭有效之條件下接觸。The method of forming an oxide according to the present disclosure may include contacting the ruthenium-containing material with steam including a ruthenium-containing precursor. The method can further include providing a water vapor generator comprising one or more inlet streams and an outlet stream, wherein the one or more inlet streams comprise hydrogen and oxygen, and wherein the one or more inlet streams are hydrogen to oxygen The ratio can be controlled. The method can still further include contacting the niobium-containing material with the outlet stream under conditions effective to form crystalline niobate pentoxide thereon.

如本文中進一步論述，可控制饋入水蒸汽產生器的一或多個入口流之氫對氧比率。因此，除了水之外，出口流亦可能包括氫。當入口流之氫對氧原子比超過6：3時，超過水蒸汽產生所需的化學計量量之氫將通過水蒸汽產生器至出口流。As discussed further herein, the hydrogen to oxygen ratio of one or more inlet streams fed to the water vapor generator can be controlled. Thus, in addition to water, the outlet stream may also include hydrogen. When the hydrogen to oxygen ratio of the inlet stream exceeds 6:3, the stoichiometric amount of hydrogen that exceeds the water vapor production will pass through the water vapor generator to the outlet stream.

在本文中描述之一或多個實施例中，可使用氣相沈積製程。在此等實施例中，氣相沈積製程可實現含釕材料(例如，含釕材料之表面)與一或多個蒸汽之接觸，其中每一蒸汽可包括下列中之一或多者：含鉭前驅物、反應氣體(例如，水)、惰性氣體或其他氣體。在本揭示案之一或多個實施例中，對形成五氧化二鉭有效之條件可包括400℃至500℃(或在一些實施例中，400℃至450℃)的用於含釕材料之表面的溫度。氣相沈積製程可實現使含釕材料與來自水蒸汽產生器之出口流接觸。另外，氣相沈積製程可為包括複數個沈積循環之原子層沈積製程。In one or more embodiments described herein, a vapor deposition process can be used. In such embodiments, the vapor deposition process can effect contact of the cerium-containing material (eg, the surface of the cerium-containing material) with one or more vapors, wherein each vapor can include one or more of the following: Precursor, reactive gas (eg, water), inert gas, or other gas. In one or more embodiments of the present disclosure, the conditions effective for forming tantalum pentoxide may include 400 ° C to 500 ° C (or in some embodiments, 400 ° C to 450 ° C) for the ruthenium containing material. The temperature of the surface. The vapor deposition process enables contacting the ruthenium containing material with the exit stream from the water vapor generator. Additionally, the vapor deposition process can be an atomic layer deposition process that includes a plurality of deposition cycles.

如本文中所論述，可控制至水蒸汽產生器的入口流之氫對氧比率。因此，在複數個沈積循環期間，有可能改變氫對氧比率。舉例而言，在複數個沈積循環期間的一或多個沈積循環期間，可使用第一氫對氧比率。隨後，在其餘沈積循環中之一或多者期間，可使用與第一氫對氧比率不同之第二氫對氧比率。As discussed herein, the hydrogen to oxygen ratio to the inlet stream of the steam generator can be controlled. Therefore, it is possible to change the hydrogen to oxygen ratio during a plurality of deposition cycles. For example, the first hydrogen to oxygen ratio can be used during one or more deposition cycles during a plurality of deposition cycles. Subsequently, during one or more of the remaining deposition cycles, a second hydrogen to oxygen ratio different from the first hydrogen to oxygen ratio may be used.

本揭示案之方法可包括氫對氧比率之一或多個改變，其中每一改變可具有任何量值。舉例而言，對於每3份氧，改變可為至少0.01份氫、至少0.1份氫、至少0.5份氫或至少1份氫(基於原子)。改變可小於或等於如由水蒸汽產生器操作限制允許的氫對氧比率之最大改變。舉例而言，對於每3份氧，改變可小於或等於2.0份氫、1.9份氫、1.5份氫或1.1份氫(基於原子)。舉例而言，在複數個沈積循環期間，氫對氧比率之改變可發生一或多次。The method of the present disclosure may include one or more changes in hydrogen to oxygen ratio, wherein each change may have any magnitude. For example, for every 3 parts of oxygen, the change can be at least 0.01 parts hydrogen, at least 0.1 parts hydrogen, at least 0.5 parts hydrogen, or at least 1 part hydrogen (based on atoms). The change may be less than or equal to the maximum change in hydrogen to oxygen ratio as allowed by the water vapor generator operating limits. For example, for every 3 parts of oxygen, the change can be less than or equal to 2.0 parts hydrogen, 1.9 parts hydrogen, 1.5 parts hydrogen, or 1.1 parts hydrogen (based on atoms). For example, a change in hydrogen to oxygen ratio may occur one or more times during a plurality of deposition cycles.

當在許多連續的沈積循環期間使氫對氧比率保持不變時，所形成之結晶五氧化二鉭可具有第一結晶取向。因此，在一或多個實施例中，有可能藉由選擇至水蒸汽產生器的入口流中之特定氫對氧比率來選擇性地形成具有特定結晶取向之結晶五氧化二鉭。舉例而言，使用至水蒸汽產生器的入口流中之氫對氧之恆定的6：3原子比，結晶五氧化二鉭之結晶取向可為c軸取向(亦即，(003)及(006)米勒指數(Miller index))。或者，至水蒸汽產生器的入口流中之氫對氧之恆定的8：3原子比可導致具有諸如(200)之取向的結晶五氧化二鉭。在包括使用至少兩個氫對氧比率的本揭示案之實施例中，使用第一氫對氧比率形成之五氧化二鉭可具有與使用第二氫對氧比率形成之五氧化二鉭的結晶取向不同之結晶取向。The crystalline pentoxide pentoxide formed may have a first crystalline orientation when the hydrogen to oxygen ratio is maintained constant during many successive deposition cycles. Thus, in one or more embodiments, it is possible to selectively form crystalline antimony pentoxide having a particular crystallographic orientation by selecting a specific hydrogen to oxygen ratio in the inlet stream to the steam generator. For example, using a constant 6:3 atomic ratio of hydrogen to oxygen in the inlet stream to the steam generator, the crystalline orientation of the crystalline antimony pentoxide can be c-axis oriented (ie, (003) and (006) ) Miller index). Alternatively, a constant 8:3 atomic ratio of hydrogen to oxygen in the inlet stream to the steam generator can result in crystalline antimony pentoxide having an orientation such as (200). In embodiments of the present disclosure that include the use of at least two hydrogen to oxygen ratios, the tantalum pentoxide formed using the first hydrogen to oxygen ratio can have a crystallization of tantalum pentoxide formed using a second hydrogen to oxygen ratio. Different orientations of crystal orientation.

第一與第二五氧化二鉭之間的取向差異可影響結晶(例如，多晶)五氧化二鉭之晶界對準。影響晶界對準可導致組合的五氧化二鉭中之減少的晶界誘發之洩漏。可在單一取向中結晶組構第一及第二結晶五氧化二鉭中之一或兩者。此外，第一及第二結晶五氧化二鉭中之一或兩者可包括不存在於另一結晶五氧化二鉭中之一個以上的結晶取向。在此等情況下，兩個材料之間的取向之改變可影響晶界對準，且可藉此減少晶界誘發之漏電流。The difference in orientation between the first and second bismuth pentoxide can affect the grain boundary alignment of the crystalline (eg, polycrystalline) antimony pentoxide. Affecting grain boundary alignment can result in reduced grain boundary induced leakage in the combined tantalum pentoxide. One or both of the first and second crystalline antimony pentoxide may be crystallized in a single orientation. Further, one or both of the first and second crystalline antimony pentoxides may include one or more crystal orientations not present in the other crystalline antimony pentoxide. In such cases, changes in orientation between the two materials can affect grain boundary alignment and thereby reduce grain boundary induced leakage current.

結晶材料(例如，五氧化二鉭)之取向可指定有米勒指數(結晶方向及平面之記數法系統)。米勒指數之解釋可見於Kingery等人之「Introduction to Ceramics」(第二版，John Wiley及Sons，紐約，NY，1976，第44至56頁)中。舉例而言，c軸取向之結晶五氧化二鉭可由米勒指數表示為(003)及/或(006)。結晶五氧化二鉭之其他結晶取向包括(但不限於)(200)、(203)、(220)及(102)取向及其他取向。The orientation of the crystalline material (e.g., tantalum pentoxide) can be specified by the Miller index (the crystallographic direction and the plane of the notation system). An explanation of the Miller Index can be found in "Introduction to Ceramics" by Kingery et al. (Second Edition, John Wiley and Sons, New York, NY, 1976, pp. 44-56). For example, the c-axis oriented crystalline antimony pentoxide can be expressed by the Miller index as (003) and/or (006). Other crystalline orientations of crystalline antimony pentoxide include, but are not limited to, (200), (203), (220), and (102) orientations and other orientations.

可使用x射線繞射技術來識別許多材料之結晶取向。可藉由低掠角入射x射線繞射(GIXRD)來實現薄結晶材料(例如，薄膜或層)之X射線繞射。此等繞射技術導致強度對2θ值之曲線。使用布拉格定律(Bragg's law)，nλ=2d sinθ，且知曉繞射束之階n、入射x射線束之波長λ及x射線束之入射角θ，吾人可計算晶格之原子之平行平面之間的距離(d間距)。視主體材料而定，此等d間距對應於特定結晶取向。X-ray diffraction techniques can be used to identify the crystallographic orientation of many materials. X-ray diffraction of thin crystalline materials (eg, films or layers) can be achieved by low grazing angle incident x-ray diffraction (GIXRD). These diffraction techniques result in a curve of intensity versus 2 theta value. Using Bragg's law, nλ = 2d sin θ, and knowing the order n of the diffraction beam, the wavelength λ of the incident x-ray beam, and the incident angle θ of the x-ray beam, we can calculate between the parallel planes of the atoms of the crystal lattice. Distance (d spacing). Depending on the host material, these d-spacings correspond to a particular crystallographic orientation.

應注意，結晶五氧化二鉭可為多晶。亦即，結晶五氧化二鉭可具有一個以上的結晶取向。在此等情況下，在本揭示案中，當提到特定結晶取向(例如，(003))時，有意將此結晶取向廣泛地解釋為包括具有彼結晶取向之單晶材料及亦具有彼取向之多晶材料，其中自2θ值判定主取向，在2θ值下，最高強度峰值位於x射線繞射掃描上。較小強度之峰值可指示可以較小程度存在之其他結晶取向。另外，可能不能將一些峰值與背景雜訊區分開，從而致使此等取向不可偵測到。It should be noted that the crystalline antimony pentoxide may be polycrystalline. That is, the crystalline antimony pentoxide may have more than one crystal orientation. In such cases, in the present disclosure, when referring to a particular crystal orientation (eg, (003)), the crystal orientation is intentionally interpreted broadly to include a single crystal material having a crystal orientation and also having an orientation. A polycrystalline material in which the main orientation is determined from the 2θ value, and at the 2θ value, the highest intensity peak is located on the x-ray diffraction scan. The peak of the smaller intensity may indicate other crystallographic orientations that may be present to a lesser extent. In addition, some peaks may not be distinguished from background noise, making these orientations undetectable.

應注意，特定氫對氧比率不需要導致所形成的結晶五氧化二鉭之單一結晶取向。雖然可能存在主取向，但五氧化二鉭可為多晶的，其具有可藉由x射線繞射分析辨別的一個以上晶體取向。It should be noted that the specific hydrogen to oxygen ratio does not require a single crystal orientation of the formed crystalline antimony pentoxide. While there may be a primary orientation, the tantalum pentoxide may be polycrystalline with more than one crystal orientation that can be discerned by x-ray diffraction analysis.

如上所提及，可以至水蒸汽產生器的入口流中之不同氫對氧比率來形成結晶五氧化二鉭之不同結晶取向。在一些實施例中，可在複數個沈積循環期間形成具有不同結晶取向之結晶五氧化二鉭。舉例而言，複數個沈積循環可包括b+c個沈積循環。在至水蒸汽產生器的入口中之第一氫對氧比率下之前b個循環期間，可形成具有第一結晶取向之第一結晶五氧化二鉭。接著，在c個額外循環期間，氫對氧比率可加以改變且隨後保持恆定地處於第二氫對氧比率下，以便形成具有第二結晶取向之第二結晶五氧化二鉭。第二結晶取向可與第一結晶取向不同。兩個不同取向之結晶五氧化二鉭可形成物品(例如，器件)之兩個部分。As mentioned above, different hydrogen to oxygen ratios in the inlet stream of the steam generator can be used to form different crystallographic orientations of crystalline antimony pentoxide. In some embodiments, crystalline bismuth pentoxide having different crystallographic orientations can be formed during a plurality of deposition cycles. For example, a plurality of deposition cycles can include b+c deposition cycles. A first crystalline antimony pentoxide having a first crystal orientation may be formed during the first b cycles of the first hydrogen to oxygen ratio in the inlet to the steam generator. Next, during c additional cycles, the hydrogen to oxygen ratio can be varied and then maintained constantly at a second hydrogen to oxygen ratio to form a second crystalline tantalum pentoxide having a second crystalline orientation. The second crystal orientation may be different from the first crystal orientation. Two different orientations of crystalline antimony pentoxide can form two parts of an article (eg, a device).

於本揭示案中使用時，有意使具有不同結晶取向之材料廣泛地包括其中x射線繞射掃描指示結晶取向之不同相對比例之材料。因此，具有不同結晶取向之材料包括具有不同主結晶取向之材料，以及具有相同主結晶取向之材料。As used in this disclosure, materials having different crystallographic orientations are intended to broadly include materials in which x-ray diffraction scans indicate different relative proportions of crystal orientation. Thus, materials having different crystal orientations include materials having different main crystal orientations, as well as materials having the same main crystal orientation.

在某些實施例中，如本文中所揭示之物品可包括第一結晶五氧化二鉭及在該第一結晶五氧化二鉭之至少一部分上的第二結晶五氧化二鉭，其中該第一五氧化二鉭具有一不同於該第二結晶五氧化二鉭之結晶取向的結晶取向。在一或多個實施例中，第一及第二結晶五氧化二鉭可相互直接接觸。換言之，第一結晶五氧化二鉭可直接處於第二結晶五氧化二鉭上。在一或多個實施例中，第一及第二結晶五氧化二鉭中之一或兩者可形成層(例如，薄膜)。結晶五氧化二鉭中之一者可為物品中之介電材料。在其中第一與第二結晶五氧化二鉭直接接觸之實施例中，五氧化二鉭可為介電材料(例如，介電層)。在其中第一與第二結晶五氧化二鉭直接接觸之一些實施例中，如與具有單一結晶取向及同等厚度之結晶五氧化二鉭相比，組合可具有高的介電常數，且可具有減少的晶界誘發之洩漏。In certain embodiments, an article as disclosed herein can include a first crystalline antimony pentoxide and a second crystalline antimony pentoxide on at least a portion of the first crystalline antimony pentoxide, wherein the first The antimony pentoxide has a crystal orientation different from the crystal orientation of the second crystalline antimony pentoxide. In one or more embodiments, the first and second crystalline antimony pentoxides can be in direct contact with each other. In other words, the first crystalline antimony pentoxide can be directly on the second crystalline antimony pentoxide. In one or more embodiments, one or both of the first and second crystalline antimony pentoxides may form a layer (eg, a film). One of the crystalline antimony pentoxides can be a dielectric material in the article. In embodiments in which the first and second crystalline antimony pentoxide are in direct contact, the antimony pentoxide may be a dielectric material (eg, a dielectric layer). In some embodiments in which the first and second crystalline antimony pentoxide are in direct contact, the combination may have a high dielectric constant, and may have a higher dielectric constant than a crystalline antimony pentoxide having a single crystal orientation and the same thickness. Reduced grain boundary induced leakage.

在某些實施例中，如本文中揭示之物品可為電容器中之介電組件或包括電容器的器件中之組件。物品可為(例如)半導體器件或記憶體器件(諸如，DRAM器件)之組件。In some embodiments, an article as disclosed herein can be a component in a capacitor or a component in a device that includes a capacitor. The article can be, for example, a component of a semiconductor device or a memory device, such as a DRAM device.

在某些實施例中，如本文中揭示之物品可包括一包括含釕材料之第一電極。該物品可進一步包括在第一電極之至少一部分上的第一結晶五氧化二鉭，其中該第一結晶五氧化二鉭具有一第一結晶取向。該物品亦可包括在第一結晶五氧化二鉭之至少一部分上的第二結晶五氧化二鉭，其中第二結晶五氧化二鉭具有與第一結晶取向不同之第二結晶取向。此物品可進一步包括在第二結晶五氧化二鉭之至少一部分上的第二電極。該第二電極亦可包括含釕材料(例如，釕金屬)。In certain embodiments, an article as disclosed herein can include a first electrode comprising a ruthenium containing material. The article can further include a first crystalline antimony pentoxide on at least a portion of the first electrode, wherein the first crystalline antimony pentoxide has a first crystal orientation. The article can also include a second crystalline antimony pentoxide on at least a portion of the first crystalline antimony pentoxide, wherein the second crystalline antimony pentoxide has a second crystalline orientation that is different from the first crystalline orientation. The article can further include a second electrode on at least a portion of the second crystalline antimony pentoxide. The second electrode may also include a ruthenium containing material (eg, ruthenium metal).

具有處於一電極上的至少兩個不同取向之結晶五氧化二鉭之物品可為電容器器件之組件。在兩個電極上或之間的此物品可為(例如)電容器器件中之組件或可為電容器器件。此等物品可應用於(例如)半導體器件、記憶體器件(例如，DRAM晶片)及其中電容器可有用的其他器件中。An article having at least two different orientations of crystalline antimony pentoxide on an electrode can be a component of a capacitor device. This article on or between the two electrodes can be, for example, a component in a capacitor device or can be a capacitor device. Such articles are applicable, for example, to semiconductor devices, memory devices (e.g., DRAM wafers), and other devices in which capacitors may be useful.

在一些實施例中，結晶五氧化二鉭具有六邊形密集結晶結構(例如，六方相)。舉例而言，在沈積時及/或在退火後，五氧化二鉭可形成於或直接形成於具有六邊形密集結構之含釕材料上以便形成結晶五氧化二鉭。在一些實施例中，五氧化二鉭可在沈積時結晶。視情況，六邊形密集結晶五氧化二鉭可經結晶組構。具體言之，結晶五氧化二鉭可在c軸取向上經結晶組構(亦即，c軸組構)。結晶五氧化二鉭亦可經a軸結晶組構((200)取向)，或可在其他取向上經結晶組構，諸如，(203)、(220)或(102)。In some embodiments, the crystalline antimony pentoxide has a hexagonal dense crystalline structure (eg, a hexagonal phase). For example, at the time of deposition and/or after annealing, tantalum pentoxide may be formed or formed directly on the ruthenium-containing material having a hexagonal dense structure to form crystalline bismuth pentoxide. In some embodiments, antimony pentoxide may crystallize upon deposition. As the case may be, the hexagonal dense crystalline antimony pentoxide may be crystallized. Specifically, the crystalline antimony pentoxide may be crystallized in a c-axis orientation (i.e., a c-axis configuration). The crystalline antimony pentoxide may also be subjected to an a-axis crystalline structure ((200) orientation), or may be crystallized in other orientations, such as (203), (220) or (102).

在包括具有第一結晶取向之第一結晶五氧化二鉭及具有與第一結晶取向不同之第二結晶取向之第二結晶五氧化二鉭的物品中，該等結晶五氧化二鉭中之至少一者可具有(003)或(006)結晶取向。在一或多個實施例中，第一或第二結晶五氧化二鉭中之至少一者可具有(200)結晶取向。該等結晶五氧化二鉭中之至少一者可具有具(203)、(220)或(102)之米勒指數之取向。In an article comprising a first crystalline antimony pentoxide having a first crystal orientation and a second crystalline antimony pentoxide having a second crystal orientation different from the first crystal orientation, at least one of the crystalline antimony pentoxides One may have a (003) or (006) crystal orientation. In one or more embodiments, at least one of the first or second crystalline antimony pentoxide may have a (200) crystalline orientation. At least one of the crystalline bismuth pentoxides may have an orientation with a Miller index of (203), (220) or (102).

根據本揭示案的形成氧化物之方法可包括使含釕材料與包括含鉭前驅物之蒸汽接觸。該方法可進一步包括使該含釕材料與包括氫及水之第二蒸汽在對於於其上形成結晶五氧化二鉭有效之條件下接觸。在此方法中，含鉭前驅物、含釕材料及結晶五氧化二鉭係如本文中所描述。The method of forming an oxide according to the present disclosure may include contacting the ruthenium-containing material with steam including a ruthenium-containing precursor. The method can further comprise contacting the niobium-containing material with a second vapor comprising hydrogen and water under conditions effective to form crystalline antimony pentoxide thereon. In this method, the ruthenium containing precursor, the ruthenium containing material, and the crystalline ruthenium pentoxide are as described herein.

在一些實施例中，包括氫及水之第二蒸汽可為水蒸汽產生器之出口流，其中至該水蒸汽產生器之入口流含有超過產生水所需的氫對氧之化學計量比之氫。或者，舉例而言，可將具有氫與氧之化學計量比之入口流饋入至水蒸汽產生器，且可將一些額外的氫添加至來自水蒸汽產生器之出口流。製造包括氫及水蒸汽之第二蒸汽的其他方法對一般熟習此項技術者將顯而易見。In some embodiments, the second vapor comprising hydrogen and water can be an outlet stream of the steam generator, wherein the inlet stream to the steam generator contains hydrogen in a stoichiometric ratio of hydrogen to oxygen required to produce water . Alternatively, for example, an inlet stream having a stoichiometric ratio of hydrogen to oxygen can be fed to the steam generator, and some additional hydrogen can be added to the outlet stream from the steam generator. Other methods of making a second vapor comprising hydrogen and water vapor will be apparent to those of ordinary skill in the art.

形成於含釕材料上之結晶五氧化二鉭可經結晶組構(例如，c軸組構)。於本文中使用時，「組構」或「經組構」通常指正論述的結晶材料之結晶取向，且不應與結晶材料之表面平滑度混淆。The crystalline ruthenium pentoxide formed on the ruthenium-containing material may be subjected to a crystalline structure (for example, a c-axis structure). As used herein, "structural" or "structural" generally refers to the crystalline orientation of the crystalline material being discussed and should not be confused with the surface smoothness of the crystalline material.

在某些實施例中，含釕材料之至少一部分為結晶的(例如，多晶)，且具有六邊形密集結晶結構。另外，含釕材料之至少一部分可經結晶組構。含釕材料亦可在c軸取向上經結晶組構(亦即，c軸組構)。In certain embodiments, at least a portion of the cerium-containing material is crystalline (eg, polycrystalline) and has a hexagonal dense crystalline structure. Additionally, at least a portion of the cerium-containing material can be crystallized. The cerium-containing material may also be crystallized in a c-axis orientation (ie, a c-axis configuration).

在一些實施例中，含釕材料可為純釕(亦即，釕金屬)。在其他實施例中，除了釕之外，含釕材料可含有其他元素，包括(但不限於)氧。釕金屬亦可為具有六邊形密集結構之結晶體。另外，釕金屬亦可經c軸組構。In some embodiments, the cerium-containing material can be pure cerium (ie, cerium metal). In other embodiments, the cerium-containing material may contain other elements, including but not limited to oxygen, in addition to cerium. The base metal may also be a crystal body having a hexagonal dense structure. In addition, base metals can also be organized by c-axis.

在本文中描述之實施例中的含釕材料可具有任何形狀或大小。一些含釕材料為可或可不為毯膜之含釕層。於本文中使用時，毯膜可為可塗布基板表面之一部分直至且包括整個基板表面之任何未經圖案化之沈積。在某些實施例中，含釕材料可為具有自100Å至300Å之厚度的層，但視特定應用而定，可按需要自此範圍內或外選擇厚度。一些含釕材料可具有較激進(aggressive)之拓撲。舉例而言，作為該基板之部分，含釕材料可採取一或多個空穴、圓柱、容器、通道、堆疊及其他半導體特徵及其組合之形式。The cerium-containing material in the embodiments described herein can have any shape or size. Some bismuth-containing materials are ruthenium-containing layers that may or may not be blankets. As used herein, a blanket film can be any unpatterned deposition of a portion of a substrate surface that can be coated up to and including the entire substrate surface. In certain embodiments, the bismuth-containing material can be a layer having a thickness from 100 Å to 300 Å, but depending on the particular application, the thickness can be selected from within or outside of this range as desired. Some bismuth-containing materials may have a more aggressive topology. For example, as part of the substrate, the germanium-containing material can take the form of one or more voids, cylinders, vessels, channels, stacks, and other semiconductor features, and combinations thereof.

如本文中描述之含釕材料可用於結晶五氧化二鉭可形成於其上之廣泛的各種各樣之應用中。舉例而言，含釕材料可為基板、半導體基板或基板總成之一部分。視情況，可將含釕材料用作電容器或閘應用中之一或多個電極。具體言之，含釕材料可為作為半導體器件(諸如，DRAM電容 器)之一或多個部分之一或多個電極。在一些實施例中，含釕材料為電容器構造中之底部電極。The rhodium-containing material as described herein can be used in a wide variety of applications in which crystalline antimony pentoxide can be formed. For example, the germanium-containing material can be part of a substrate, a semiconductor substrate, or a substrate assembly. Optionally, the ruthenium containing material can be used as one or more electrodes in a capacitor or gate application. In particular, the germanium-containing material can be used as a semiconductor device (such as a DRAM capacitor). One or more of one or more electrodes. In some embodiments, the germanium containing material is the bottom electrode in a capacitor construction.

通常，含釕材料易於氧化。在多數實施例中，含釕材料包括至少一含氧表面。含氧表面亦可含有其他元素，包括(但不限於)釕。含氧表面可包括氧化釕RuOx (例如，RuO2 )。在一些實施例中，含釕材料之至少一部分之氧化可發生於在其上形成結晶五氧化二鉭之前、期間及/或之後，以在表面之至少一部分上形成氧化釕。Generally, the cerium-containing material is susceptible to oxidation. In most embodiments, the cerium-containing material includes at least one oxygen-containing surface. The oxygen-containing surface may also contain other elements including, but not limited to, hydrazine. The oxygen-containing surface may include ruthenium oxide RuO x (eg, RuO 2 ). In some embodiments, oxidation of at least a portion of the cerium-containing material can occur before, during, and/or after formation of crystalline pentoxide pentoxide to form cerium oxide on at least a portion of the surface.

在含釕材料上的經組構之結晶五氧化二鉭之成核對含釕材料之表面很敏感。具體言之，在含釕材料之含氧表面中的氧之顯著含量可導致難以於其上形成結晶組構之結晶五氧化二鉭(見，例如，Cho等人之Microelectronic Engineering ，80：317-320(2005))。基於原子濃度，含氧表面中的40原子百分比或更大百分比之氧的濃度將可能導致難以於其上使結晶五氧化二鉭層成核。另一方面，含氧表面中之氧濃度減少至20原子百分比或更小允許可視情況經結晶組構的結晶五氧化二鉭之成核。The nucleation of the structured crystalline antimony pentoxide on the cerium-containing material is sensitive to the surface of the cerium-containing material. In particular, the significant amount of oxygen in the oxygen-containing surface of the cerium-containing material can result in crystalline pentoxide pentoxide which is difficult to form a crystalline structure thereon (see, for example, Chi et al., Microelectronic Engineering , 80:317- 320 (2005)). Based on the atomic concentration, a concentration of 40 atomic percent or more of oxygen in the oxygen-containing surface will likely result in difficulty in nucleating the crystalline antimony pentoxide layer thereon. On the other hand, the reduction of the oxygen concentration in the oxygen-containing surface to 20 atomic percent or less allows nucleation of the crystalline antimony pentoxide, which may optionally be crystallized.

為了在具有至少一含氧表面之含釕材料上形成結晶五氧化二鉭，需要自含氧表面移除至少一些氧。此可藉由使含氧表面與處理組合物在對移除至少一些氧有效之條件下接觸來實現。此等處理組合物包括(例如)水，且自含釕材料之含氧表面移除至少一些氧之方法揭示於2007年12月18日申請之美國專利申請案第11/958,952號(Bhat等人)中(現為美國專利申請公開案第2009/0155486號)。在本揭示案中，其中揭示之此等方法可用以製備含釕材料之表面，以便在於其上形成結晶五氧化二鉭之前自其移除至少一些氧。In order to form crystalline antimony pentoxide on a cerium-containing material having at least one oxygen-containing surface, it is desirable to remove at least some of the oxygen from the oxygen-containing surface. This can be accomplished by contacting the oxygen-containing surface with the treatment composition under conditions effective to remove at least some of the oxygen. Such treatment compositions include, for example, water, and the method of removing at least some of the oxygen from the oxygen-containing surface of the ruthenium-containing material is disclosed in U.S. Patent Application Serial No. 11/958,952, filed on Dec. ) (now US Patent Application Publication No. 2009/0155486). In the present disclosure, such methods disclosed therein can be used to prepare a surface comprising a ruthenium material to remove at least some of the oxygen therefrom prior to forming crystalline ruthenium pentoxide thereon.

一些實施例允許移除氧且接觸以形成結晶五氧化二鉭於原地發生。在此等實施例中，自含釕材料之表面移除至少一些氧與在其上形成結晶五氧化二鉭之方法可發生於同一沈積腔室中。視情況，在其他實施例中，氧之移除及形成五氧化二鉭可於外部發生。在此等實施例中，可在氧之移除與五氧化二鉭之形成之間移動含釕材料，包括移動至一或多個其他沈積腔室。Some embodiments allow oxygen to be removed and contacted to form crystalline antimony pentoxide in situ. In such embodiments, the removal of at least some of the oxygen from the surface of the ruthenium containing material and the formation of crystalline ruthenium pentoxide thereon may occur in the same deposition chamber. Optionally, in other embodiments, the removal of oxygen and the formation of antimony pentoxide may occur externally. In such embodiments, the ruthenium containing material can be moved between the removal of oxygen and the formation of tantalum pentoxide, including movement to one or more other deposition chambers.

如上所提及，可控制至水蒸汽產生器的入口流中之氫對氧比率，從而允許(例如)過剩的氫或氧通過水蒸汽產生器且接觸含釕材料之表面。然而，由於含釕材料之表面的氧化趨勢(藉此導致難以於其上形成結晶五氧化二鉭)，可控制氫對氧比率以避免將過剩氧引入至含釕材料之表面。As mentioned above, the ratio of hydrogen to oxygen in the inlet stream to the steam generator can be controlled to allow, for example, excess hydrogen or oxygen to pass through the water vapor generator and contact the surface of the cerium-containing material. However, due to the tendency of oxidation of the surface of the cerium-containing material, thereby making it difficult to form crystalline bismuth pentoxide thereon, the hydrogen to oxygen ratio can be controlled to avoid introducing excess oxygen to the surface of the cerium-containing material.

結晶五氧化二鉭之形成為材料提供可用於需要高k常數材料之任何應用中之介電常數。詳言之，可將結晶五氧化二鉭用作介電材料，尤其用作基板、半導體基板及基板總成上之一或多個介電層。作為高k常數材料之結晶五氧化二鉭亦可用作半導體器件之一或多個介電部分，諸如，DRAM單元中之電容器或閘極。在某些實施例中，結晶五氧化二鉭具有40至110之介電常數。在某些其他實施例中，結晶五氧化二鉭具有至少50之介電常數。在某些實施例中，結晶五氧化二鉭(例如，結晶五氧化二鉭材料或層)可具有50(埃)至200之厚度，但視特定應用而定，可自此範圍內或外選擇厚度。舉例而言，結晶五氧化二鉭之厚度可為50至150或90至150。在具有第一結晶取向之第一結晶五氧化二鉭形成於具有第二結晶取向之第二結晶五氧化二鉭上或與其直接接觸之實施例中，第一及第二結晶五氧化二鉭(例如，材料或層)中之每一者可具有任何厚度，但至多為150(例如，50至150或50至90)，且組合厚度可至多為150，但視特定應用而定，可自此範圍內或外選擇每一結晶五氧化二鉭之厚度以及組合之厚度。The formation of crystalline antimony pentoxide provides the material with a dielectric constant that can be used in any application requiring a high k constant material. In particular, crystalline antimony pentoxide can be used as a dielectric material, particularly as one or more dielectric layers on a substrate, a semiconductor substrate, and a substrate assembly. Crystalline antimony pentoxide, which is a high-k constant material, can also be used as one or more dielectric portions of a semiconductor device, such as a capacitor or gate in a DRAM cell. In certain embodiments, the crystalline antimony pentoxide has a dielectric constant of 40 to 110. In certain other embodiments, the crystalline antimony pentoxide has a dielectric constant of at least 50. In certain embodiments, crystalline antimony pentoxide (eg, crystalline antimony pentoxide material or layer) can have 50 (A) to 200 Thickness, but depending on the particular application, the thickness can be selected from within or outside this range. For example, the thickness of the crystalline antimony pentoxide can be 50. To 150 Or 90 To 150 . In the embodiment in which the first crystalline antimony pentoxide having the first crystal orientation is formed on or in direct contact with the second crystalline antimony pentoxide having the second crystal orientation, the first and second crystalline antimony pentoxides ( For example, each of the materials or layers can have any thickness, but at most 150 (for example, 50 To 150 Or 50 To 90 ), and the combined thickness can be up to 150 However, depending on the particular application, the thickness of each crystalline tantalum pentoxide and the thickness of the combination can be selected from within or outside this range.

在一些實施例中，結晶五氧化二鉭形成於毯膜拓撲上。在其他實施例中，結晶五氧化二鉭可形成於激進拓撲上，諸如，形成於具有包括(但不限於)堆疊、圓柱、容器及開口之一或多個特徵的DRAM單元上。結晶五氧化二鉭可形成為一層(諸如，介電層)。所形成之結晶五氧化二鉭可為可用於介電器件之任何大小。In some embodiments, crystalline antimony pentoxide is formed on the blanket topology. In other embodiments, crystalline antimony pentoxide may be formed on a radical topology, such as on a DRAM cell having one or more features including, but not limited to, stacks, cylinders, vessels, and openings. The crystalline antimony pentoxide can be formed into a layer (such as a dielectric layer). The crystalline pentoxide pentoxide formed can be of any size that can be used for dielectric devices.

在多數實施例中的形成之結晶五氧化二鉭為實質上無雜質之五氧化二鉭。於本文中使用時，「實質上無」雜質意謂在結晶五氧化二鉭中可存在不超過可忽略量的雜質(例如，小於1原子百分比)。The crystalline pentoxide pentoxide formed in most of the examples is bismuth pentoxide substantially free of impurities. As used herein, "substantially free" impurities means that no more than a negligible amount of impurities (e.g., less than 1 atomic percent) may be present in the crystalline antimony pentoxide.

非晶五氧化二鉭之形成可繼之以退火，其持續0.5分鐘至2小時之一或多個時間段，且通常涉及500℃至1000℃之溫度。在一或多個實施例中，本揭示案之方法不包括退火。沈積時結晶五氧化二鉭可形成於含釕材料之表面上。亦即，可以結晶結構而非非晶狀態形成五氧化二鉭。亦即，在本揭示案之一或多個實施例中，可在無退火之情況下形成一或多個結晶五氧化二鉭(例如，第一及第二結晶五氧化二鉭)。另外，在其他實施例中，沈積時結晶五氧化二鉭可為沈積時諸如在c軸取向上(亦即，經c軸組構)經結晶組構之結晶五氧化二鉭。當不需要退火來使所形成之五氧化二鉭結晶時，結晶五氧化二鉭形成於其上的表面(例如，含釕材料之表面)之溫度可保持小於或等於500℃，且在一些實施例中，小於或等於450℃。當不需要退火來使所形成之五氧化二鉭結晶時，結晶五氧化二鉭形成於其上的表面(例如，含釕材料之表面)之溫度可保持大於或等於375℃，且在一些實施例中，大於或等於400℃。The formation of amorphous bismuth pentoxide may be followed by annealing, which lasts for one to more than one hour or more, and typically involves a temperature of from 500 °C to 1000 °C. In one or more embodiments, the methods of the present disclosure do not include annealing. Crystalline pentoxide can be formed on the surface of the cerium-containing material during deposition. That is, tantalum pentoxide can be formed in a crystalline structure rather than an amorphous state. That is, in one or more embodiments of the present disclosure, one or more crystalline antimony pentoxides (eg, first and second crystalline antimony pentoxides) may be formed without annealing. Additionally, in other embodiments, the crystalline bismuth pentoxide may be deposited upon deposition such as crystalline bismuth pentoxide in a c-axis orientation (i.e., via a c-axis configuration). When annealing is not required to crystallize the formed antimony pentoxide, the temperature of the surface on which the crystalline antimony pentoxide is formed (for example, the surface of the antimony-containing material) may be kept less than or equal to 500 ° C, and in some implementations In the example, it is less than or equal to 450 °C. When annealing is not required to crystallize the formed antimony pentoxide, the temperature of the surface on which the crystalline antimony pentoxide is formed (for example, the surface of the antimony-containing material) may be maintained at 375 ° C or higher, and in some implementations In the example, it is greater than or equal to 400 ° C.

可將五氧化二鉭沈積於具有六邊形密集結構之含釕材料之表面上以形成結晶五氧化二鉭(例如，結晶五氧化二鉭材料或層)。具有含釕材料及結晶五氧化二鉭之此等構造可用作其中電極包括含釕材料且結晶五氧化二鉭形成介電層的電容器(例如，DRAM應用)之部分或用作製造其之中間物。包括含釕材料之電極可具有毯膜拓撲或可具有較激進之拓撲，諸如，DRAM拓撲。五氧化二鉭可為沈積時結晶的。在某些實施例中，五氧化二鉭具有六邊形結構。在某些實施例中，五氧化二鉭(例如，金屬或層)具有至少50之介電常數。視情況，第二電極可形成於結晶五氧化二鉭(例如，五氧化二鉭介電材料)之至少一部分上。第二電極可包括已知用於用作電極之廣泛的各種各樣之材料。舉例而言，此等材料可包括(但不限於)銥、釕、氮化鈮、氮化鉭、氮化鉿，及其組合。Bismuth pentoxide may be deposited on the surface of the cerium-containing material having a hexagonal dense structure to form crystalline bismuth pentoxide (e.g., crystalline pentoxide material or layer). Such a structure having a ruthenium-containing material and crystalline ruthenium pentoxide can be used as part of a capacitor (for example, a DRAM application) in which an electrode includes a ruthenium-containing material and crystalline ruthenium pentoxide forms a dielectric layer or is used as a middle portion for manufacturing Things. The electrode comprising the germanium containing material may have a blanket topology or may have a more aggressive topology, such as a DRAM topology. Antimony pentoxide can be crystallized upon deposition. In certain embodiments, the tantalum pentoxide has a hexagonal structure. In certain embodiments, tantalum pentoxide (eg, a metal or layer) has a dielectric constant of at least 50. Optionally, the second electrode can be formed on at least a portion of the crystalline antimony pentoxide (eg, a tantalum pentoxide dielectric material). The second electrode can comprise a wide variety of materials known for use as electrodes. For example, such materials can include, but are not limited to, tantalum, niobium, tantalum nitride, tantalum nitride, tantalum nitride, and combinations thereof.

提供下列實例以進一步說明本揭示案之各種特定實施例及技術。然而，應理解，可進行一般熟習此項技術者理解之許多變化及修改，同時仍處於本揭示案之範疇內。因此，本揭示案之範疇並不意欲受下列實例限制。The following examples are provided to further illustrate various specific embodiments and techniques of the present disclosure. However, it should be understood that many variations and modifications can be made by those skilled in the art, and are still within the scope of the present disclosure. Accordingly, the scope of the disclosure is not intended to be limited by the following examples.

實例構造10示意性地說明於圖1中。構造10包括在含釕材料30之至少一部分上的結晶五氧化二鉭40。含釕材料30可為一層，且可具有任何合適厚度。在一些實施例中，含釕材料30具有100至300之厚度。在一些實施例中，含釕材料30之至少表面為釕，且具有c軸結晶組構之六邊形密集結構。視情況，構造10可包括包括氧的含釕材料30之表面(未圖示)。可自含釕材料30之表面移除氧之至少一部分。構造10進一步包括在含釕材料30之表面之至少一部分上的結晶五氧化二鉭40，已在自含釕材料30之表面移除氧之至少一部分後沈積結晶五氧化二鉭40。於本文中使用時，「層」意欲包括半導體行業所特有之層，諸如(但明顯不限於)障壁層、介電層(亦即，具有高介電常數之層)及導電層。術語「層」與在半導體行業中頻繁使用之術語「膜」同義。術語「層」意欲包括在半導體技術外之技術(諸如，玻璃上塗布)中可見之層。舉例而言，此等層可直接形成於光纖、電線等上，其為不同於半導體基板之基板。另外，層可形成於(例如，直接形成於)基板之最下半導體表面上，或其可形成於如在(例如)經圖案化之晶圓中的各種各樣之層(例如，表面)中之任一者上。於本文中使用時，層不必為連續的，且在某些實施例中，為不連續的。除非另有陳述，否則於本文中使用時，「鄰近」一表面(或另一層)或在一表面(或另一層)「上」之層或材料意欲廣泛地解釋為不僅包括具有直接在表面上之層或材料之構造，且亦包括表面及層或材料由一或多個額外層(例如，層)分開之構造。於本文中使用時，除非另有陳述，否則，「直接在第二材料上」及「直接與第二材料接觸」之第一材料意欲經廣泛地解釋為包括其中第一材料之至少一部分直接與第二材料之至少一部分接觸之構造，在兩個材料之接觸部分之間無***材料。Example construction 10 is schematically illustrated in FIG. Construction 10 includes crystalline antimony pentoxide 40 on at least a portion of niobium containing material 30. The bismuth-containing material 30 can be a single layer and can have any suitable thickness. In some embodiments, the bismuth-containing material 30 has 100 Up to 300 The thickness. In some embodiments, at least the surface of the cerium-containing material 30 is tantalum and has a hexagonal dense structure of a c-axis crystalline structure. As the case may be, the construction 10 may include a surface (not shown) of the cerium-containing material 30 including oxygen. At least a portion of the oxygen may be removed from the surface of the bismuth containing material 30. The construction 10 further includes crystalline antimony pentoxide 40 on at least a portion of the surface of the niobium containing material 30 that has been deposited to remove crystalline antimony pentoxide 40 after at least a portion of the oxygen is removed from the surface of the niobium containing material 30. As used herein, "layer" is intended to include layers that are unique to the semiconductor industry, such as, but not limited to, a barrier layer, a dielectric layer (i.e., a layer having a high dielectric constant), and a conductive layer. The term "layer" is synonymous with the term "film" that is frequently used in the semiconductor industry. The term "layer" is intended to include layers that are visible in techniques other than semiconductor technology, such as coating on glass. For example, the layers can be formed directly on an optical fiber, wire, or the like, which is a substrate different from the semiconductor substrate. Additionally, a layer can be formed (eg, formed directly on) the lowermost semiconductor surface of the substrate, or it can be formed in a variety of layers (eg, surfaces), such as in, for example, a patterned wafer. Any of them. As used herein, the layers need not be continuous, and in some embodiments, discontinuous. Unless otherwise stated, a layer or material "on" a surface (or another layer) or "on" a surface (or another layer) is intended to be interpreted broadly to include not only having a surface directly The construction of layers or materials, and also includes surfaces and layers or materials that are separated by one or more additional layers (eg, layers). As used herein, unless otherwise stated, the first material "directly on the second material" and "directly in contact with the second material" is intended to be interpreted broadly to include the inclusion of at least a portion of the first material directly. The configuration in which at least a portion of the second material contacts, there is no intervening material between the contact portions of the two materials.

含釕材料30可形成或沈積於(例如)基板(例如，半導體基板或基板總成)上，該基板未說明於圖1中。於本文中使用時，「半導體基板」或「基板總成」係指諸如基底半導體材料之半導體基板或具有形成於其上之一或多個材料、結構或區域之半導體基板。基底半導體材料通常為晶圓上之最下部矽材料或沈積於另一材料上之矽材料，諸如，藍寶石上之矽。當提及基板總成時，先前已使用各種製程步驟來形成或界定區域、接面、各種結構或特徵及開口，諸如，電晶體、有效區、擴散、植入之區域、通道、接觸開口、高縱橫比開口、電容器板、電容器之障壁等。The germanium-containing material 30 can be formed or deposited on, for example, a substrate (eg, a semiconductor substrate or substrate assembly), which is not illustrated in FIG. As used herein, "semiconductor substrate" or "substrate assembly" refers to a semiconductor substrate such as a base semiconductor material or a semiconductor substrate having one or more materials, structures or regions formed thereon. The base semiconductor material is typically the lowermost tantalum material on the wafer or tantalum material deposited on another material, such as tantalum on sapphire. When referring to a substrate assembly, various process steps have been previously used to form or define regions, junctions, various structures or features, and openings, such as transistors, active regions, diffusion, implanted regions, vias, contact openings, High aspect ratio openings, capacitor plates, barriers for capacitors, etc.

本揭示案之合適的基板材料包括導電材料、半導體材料、導電金屬氮化物、導電金屬、導電金屬氧化物等。基板可為半導體基板或基板總成。可預期廣泛的各種各樣之半導體材料，諸如，硼磷矽玻璃(BPSG)；諸如導電摻雜多晶矽、單晶矽等之矽(對於本揭示案，適當形式之矽簡稱為「矽」)，例如，呈矽晶圓之形式；四乙基正矽酸鹽(TEOS)氧化物；旋塗式玻璃(亦即，SiO2 ，視情況經摻雜，藉由旋塗製程沈積)；TiN；TaN；W；Ru；Al；Cu；貴金屬等。基板總成亦可包括包括鉑、銥、氧化銥、銠、釕、氧化釕、釕酸鍶、鎳酸鑭、氮化鈦、氮化鉭、氮化鉭矽、二氧化矽、鋁、砷化鎵、玻璃等，及在半導體構造(諸如，動態隨機存取記憶體(DRAM)器件、靜態隨機存取記憶體(SRAM)器件及鐵電記憶體(FERAM)器件)中使用之其他現有或待開發之材料之部分。Suitable substrate materials for the present disclosure include conductive materials, semiconductor materials, conductive metal nitrides, conductive metals, conductive metal oxides, and the like. The substrate can be a semiconductor substrate or a substrate assembly. A wide variety of semiconductor materials are contemplated, such as borophosphon glass (BPSG); such as conductive doped polysilicon, single crystal germanium, etc. (for the present disclosure, the appropriate form is simply referred to as "矽"), For example, in the form of a germanium wafer; tetraethyl orthosilicate (TEOS) oxide; spin-on glass (ie, SiO 2 , optionally doped, deposited by a spin coating process); TiN; TaN ;W; Ru; Al; Cu; precious metals, and the like. The substrate assembly may also include platinum, rhodium, iridium oxide, ruthenium, osmium, iridium oxide, ruthenium ruthenate, strontium nickelate, titanium nitride, tantalum nitride, tantalum nitride, hafnium oxide, aluminum, arsenic. Gallium, glass, etc., and other existing or pending uses in semiconductor constructions such as dynamic random access memory (DRAM) devices, static random access memory (SRAM) devices, and ferroelectric memory (FERAM) devices Part of the material developed.

對於包括半導體基板或基板總成之基板，含釕材料30可形成於或直接形成於基板之最下部半導體表面上，或其可形成於(例如)如在經圖案化之晶圓中的各種各樣的其他表面中之任一者上。For a substrate comprising a semiconductor substrate or substrate assembly, the germanium-containing material 30 can be formed or formed directly on the lowermost semiconductor surface of the substrate, or it can be formed, for example, as in various patterned wafers. On any of the other surfaces.

不同於半導體基板或基板總成之基板亦可用於當前揭示之方法中。可使用可在其上有利地形成含釕材料30之任何基板，此等基板包括(例如)光纖、電線等。Substrates other than a semiconductor substrate or substrate assembly can also be used in the methods disclosed herein. Any substrate on which the germanium-containing material 30 can be advantageously formed can be used, such as, for example, optical fibers, wires, and the like.

可藉由各種各樣之沈積方法來形成如本文中描述之含金屬材料(例如，含釕材料及/或含結晶五氧化二鉭材料)，該等方法包括(例如)汽化、物理氣相沈積(PVD或濺鍍)及/或氣相沈積方法，諸如，化學氣相沈積(CVD)或原子層沈積(ALD)。Metal-containing materials (eg, ruthenium-containing materials and/or crystalline ruthenium pentoxide-containing materials) as described herein can be formed by a variety of deposition methods including, for example, vaporization, physical vapor deposition (PVD or sputtering) and/or vapor deposition methods such as chemical vapor deposition (CVD) or atomic layer deposition (ALD).

在本揭示案中描述之各種實施例中，含金屬前驅物組合物可用以形成含金屬材料(例如，含釕材料及/或含五氧化二鉭材料)。於本文中使用時，「含金屬」用以指可完全由金屬組成或可包括除了金屬之外的其他元素之材料，通常為化合物或層。典型的含金屬化合物包括(但不限於)金屬、金屬配位體錯合物、金屬鹽、有機金屬化合物，及其組合。典型的含金屬層包括(但不限於)金屬、金屬氧化物、金屬氮化物，及其組合。In various embodiments described in this disclosure, the metal-containing precursor composition can be used to form a metal-containing material (eg, a cerium-containing material and/or a cerium oxide-containing material). As used herein, "metal-containing" is used to mean a material that may consist entirely of or may include other elements than metals, typically a compound or layer. Typical metal-containing compounds include, but are not limited to, metals, metal ligand complexes, metal salts, organometallic compounds, and combinations thereof. Typical metal containing layers include, but are not limited to, metals, metal oxides, metal nitrides, and combinations thereof.

各種含金屬化合物可用於各種組合中，視情況藉由一或多種有機溶劑(特別對於CVD製程)，以形成含金屬前驅物組合物。本文中揭示的含金屬化合物中之一些可在不添加溶劑之情況下用於ALD中。於本文中使用時，「前驅物」及「前驅物組合物」係指可用於單獨或與其他前驅物組合物(或反應物)一起在沈積製程中在基板總成上形成材料之組合物。另外，熟習此項技術者將認識到，所使用的前驅物之類型及量將視待使用氣相沈積製程最終形成的材料之含量而定。在如本文中描述之方法之某些實施例中，前驅物組合物在汽化溫度下為液體，且有時在室溫下為液體。Various metal-containing compounds can be used in various combinations, optionally with one or more organic solvents (particularly for CVD processes) to form metal-containing precursor compositions. Some of the metal-containing compounds disclosed herein can be used in ALD without the addition of a solvent. As used herein, "precursor" and "precursor composition" mean a composition that can be used to form a material on a substrate assembly, either alone or in combination with other precursor compositions (or reactants), in a deposition process. Additionally, those skilled in the art will recognize that the type and amount of precursor used will depend on the amount of material ultimately to be formed using the vapor deposition process. In certain embodiments of the methods as described herein, the precursor composition is liquid at the vaporization temperature and is sometimes liquid at room temperature.

前驅物組合物可在室溫下為液體或固體，且對於某些實施例，在汽化溫度下為液體。通常，其為具有足夠揮發性以使用已知氣相沈積技術而使用之液體。然而，作為固體，其亦可具有足夠揮發性使得可使用已知氣相沈積技術使其自固體狀態汽化或昇華。若其為揮發性較差之固體，則其可充分地可溶於有機溶劑中或具有低於其分解溫度之熔點，使得其可用於(例如)驟汽化、起泡、微滴形成技術等中。The precursor composition can be liquid or solid at room temperature and, for certain embodiments, liquid at vaporization temperatures. Typically, it is a liquid that is sufficiently volatile to be used using known vapor deposition techniques. However, as a solid, it may also be sufficiently volatile such that it can be vaporized or sublimed from a solid state using known vapor deposition techniques. If it is a less volatile solid, it may be sufficiently soluble in the organic solvent or have a melting point below its decomposition temperature, making it useful, for example, in flash vaporization, foaming, droplet formation techniques, and the like.

本文中，可單獨或視情況與其他含金屬化合物之汽化之分子一起或視情況與汽化之溶劑分子或惰性氣體分子(若使用)一起使用汽化之含金屬化合物。於本文中使用時，「液體」指溶液或純的液體(在室溫下之液體或在高溫下熔化的處於室溫下之固體)。於本文中使用時，「溶液」不需要固體之完全的溶解，而可允許一些未溶解之固體，只要存在由有機溶劑轉遞至汽相以供用於化學氣相沈積處理之足夠量之固體即可。若在沈積中使用溶劑稀釋，則亦可將所產生的溶劑蒸汽之總莫耳濃度看作惰性載氣。Herein, the vaporized metal-containing compound may be used alone or as appropriate with other vaporized molecules of the metal-containing compound or, as appropriate, with vaporized solvent molecules or inert gas molecules, if used. As used herein, "liquid" refers to a solution or a pure liquid (a liquid at room temperature or a solid at room temperature that melts at a high temperature). As used herein, "solution" does not require complete dissolution of the solid, but may allow some undissolved solids, as long as there is a sufficient amount of solids to be transferred from the organic solvent to the vapor phase for chemical vapor deposition treatment. can. If solvent dilution is used in the deposition, the total molar concentration of the solvent vapor produced can also be considered as an inert carrier gas.

於本文中使用時，「惰性氣體」或「非反應性氣體」為通常不與其接觸的組份反應之任何氣體。舉例而言，惰性氣體通常選自包括氮、氬、氦、氖、氰、氙、任何其他非反應性氣體及其混合物之群。此等惰性氣體通常用於如本文中描述之一或多個沖洗製程中，且在一些實施例中，亦可用以輔助前驅物蒸汽輸送。As used herein, "inert gas" or "non-reactive gas" is any gas that reacts with components that are not normally in contact with it. For example, the inert gas is typically selected from the group consisting of nitrogen, argon, helium, neon, cyanide, cesium, any other non-reactive gas, and mixtures thereof. Such inert gases are typically used in one or more of the processing processes as described herein and, in some embodiments, may also be used to assist in precursor vapor transport.

適合用於如本文中描述之方法的某些實施例之溶劑可為下列中之一或多者：脂族烴或不飽和烴(C3-C20，且在某些實施例中，C5-C10，環、分支或直鏈)、芳族烴(C5-C20，且在某些實施例中，C5-C10)、鹵化烴、諸如烷基矽烷之矽烷化烴、烷基矽酸鹽、醚、環醚(例如，四氫呋喃THF)、聚醚、硫醚、酯、內酯、腈、矽油或含有以上中之任何者之組合的化合物或以上中之一或多者之混合物。該等化合物亦通常彼此相容，使得可變量的含金屬化合物之混合物將不相互作用而顯著改變其物理特性。Solvents suitable for use in certain embodiments of the methods as described herein can be one or more of the following: an aliphatic or unsaturated hydrocarbon (C3-C20, and in certain embodiments, C5-C10, Ring, branched or linear), aromatic hydrocarbons (C5-C20, and in certain embodiments, C5-C10), halogenated hydrocarbons, alkylene hydrocarbons such as alkyl decane, alkyl phthalates, ethers, rings An ether (e.g., tetrahydrofuran THF), a polyether, a thioether, an ester, a lactone, a nitrile, an eucalyptus oil, or a compound containing a combination of any of the foregoing or a mixture of one or more of the foregoing. The compounds are also generally compatible with each other such that a variable mixture of metal-containing compounds will not significantly interact to change their physical properties.

如本文中描述之方法使用金屬前驅物化合物。於本文中使用時，「金屬前驅物化合物」用以指可在原子層沈積方法中提供金屬源之化合物。另外，在一些實施例中，方法包括「金屬-有機」前驅物化合物。術語「金屬-有機」意欲廣泛地解釋為指除了金屬之外包括有機基團(亦即，含碳之基團)的化合物。因此，術語「金屬-有機」包括(但不限於)有機金屬化合物、金屬配位體錯合物、金屬鹽，及其組合。A metal precursor compound is used as described herein. As used herein, "metal precursor compound" is used to mean a compound that provides a source of metal in an atomic layer deposition process. Additionally, in some embodiments, the method includes a "metal-organic" precursor compound. The term "metal-organic" is intended to be broadly interpreted to mean a compound comprising an organic group (i.e., a carbon-containing group) in addition to a metal. Thus, the term "metal-organic" includes, but is not limited to, organometallic compounds, metal ligand complexes, metal salts, and combinations thereof.

製造含釕材料之方法在此項技術中係熟知的。例如，見美國專利第7,018,675號(Yang)、第6,784,504號(Derderian等人)及第6,074,945號(Vaartstra等人)。舉例而言，美國專利第7,018,675號(Yang)揭示一種形成釕金屬層之方法，其包括在一腔室中提供釕前驅物(例如，選自由三羰基-1,3-環己二烯釕、雙乙基環戊二烯基釕及辛二酸釘組成之群)及氧以形成氧化釕層；及在存在富氫氣體的情況下加熱氧化釕層以將該氧化釕層轉換為表面平滑之釕金屬層。對於另一實例，美國專利第6,074,945號(Vaartstra等人)揭示一種方法，其包括提供一半導體基板或基板總成；提供包括式(二烯)Ru(CO)3 之一或多種化合物之液態前驅物組合物，其中「二烯」指直鏈、分支或環狀二烯、雙環二烯、三環二烯、其衍生物(包括鹵化物、Si、S、Se、P、As、N或O雜原子或該等雜原子之組合)；使該液態前驅物組合物汽化以形成汽化之前驅物組合物；及朝向半導體基板或基板總成引導汽化之前驅物組合物以在半導體基板或基板總成之表面上形成釕金屬膜。Methods of making ruthenium containing materials are well known in the art. See, for example, U.S. Patent Nos. 7,018,675 (Yang), 6,784,504 (Derderian et al.) and 6,074,945 (Vaartstra et al.). No. 7,018,675 (Yang) discloses a method of forming a base metal layer comprising providing a hafnium precursor in a chamber (eg, selected from the group consisting of tricarbonyl-1,3-cyclohexadienium, a group consisting of bisethylcyclopentadienyl ruthenium and suberic acid nails and oxygen to form a ruthenium oxide layer; and heating the ruthenium oxide layer in the presence of a hydrogen-rich gas to convert the ruthenium oxide layer into a smooth surface钌 metal layer. For another example, US Patent No. 6,074,945 (Vaartstra et al.) discloses a method comprising providing a semiconductor substrate or substrate assembly; providing a liquid precursor comprising one or more compounds of the formula (diene) Ru(CO) 3 Composition, wherein "diene" means a linear, branched or cyclic diene, a bicyclic diene, a tricyclodiene, a derivative thereof (including a halide, Si, S, Se, P, As, N or O) a heteroatom or a combination of the heteroatoms; vaporizing the liquid precursor composition to form a vaporized precursor composition; and directing the vaporized precursor composition toward the semiconductor substrate or substrate assembly to total the semiconductor substrate or substrate A tantalum metal film is formed on the surface.

可使用氣相沈積方法自廣泛的各種各樣之含釕前驅物化合物形成含釕材料。此項技術中已知之含釕前驅物化合物包括(例如)有機釕錯合物，諸如，雙(環戊二烯基)釕(Ru(C5 H5 )2 )，及羰基釕，諸如，Ru(CO)5 、Ru2 (CO)9 、Ru3 (CO)12 、三羰基(1,3-環己二烯)釕、三羰基(環戊二烯基)-釕，及其組合，如(例如)在美國專利第7,256,123號(Derderian等人)及第7,262,132號(Marsh)及美國專利申請公開案第2005/0238808號(Gatineau等人)中所描述。可使用諸如四氯化釕(RuCl4 )、三氯化釕(RuCl3 )、五氟化釕(RuF5 )及其組合之鹵化釕化合物，如(例如)在美國專利第7,256,123號(Derderian等人)中所描述。A vapor-containing deposition method can be used to form a ruthenium-containing material from a wide variety of ruthenium-containing precursor compounds. The ruthenium-containing precursor compounds known in the art include, for example, organic ruthenium complexes such as bis(cyclopentadienyl)ruthenium (Ru(C 5 H 5 ) 2 ), and ruthenium carbonyl such as Ru (CO) 5 , Ru 2 (CO) 9 , Ru 3 (CO) 12 , tricarbonyl (1,3-cyclohexadiene) fluorene, tricarbonyl (cyclopentadienyl)-hydrazine, and combinations thereof, such as It is described, for example, in U.S. Patent No. 7,256,123 (Derderian et al.) and U.S. Patent No. 7,262,132 (Marsh) and U.S. Patent Application Publication No. 2005/0238808 (Gatineau et al.). A ruthenium halide compound such as ruthenium tetrachloride (RuCl 4 ), ruthenium trichloride (RuCl 3 ), ruthenium pentafluoride (RuF 5 ), and combinations thereof may be used, for example, in U.S. Patent No. 7,256,123 (Derderian et al. As described in person).

可使用氣相沈積方法自廣泛的各種各樣之含鉭前驅物化合物形成結晶五氧化二鉭，包括含五氧化二鉭之層。此項技術中已知之含鉭前驅物化合物包括(例如)甲氧化鉭(Ta(OMe)5 )；乙氧化鉭(Ta(OEt)5 )；丁氧化鉭(Ta(OBu)5 )；式TaX5 之鹵化鉭(其中每一X獨立地為鹵基)，諸如，氟化鉭(TaF5 )、氯化鉭(TaCl5 )及碘化鉭(TaI5 )；五(二甲胺基)鉭、三(二乙胺基)(乙基亞胺基)鉭、三(二乙胺基)(第三丁基亞胺基)鉭；其他含鉭前驅物化合物，如在美國專利第7,030,042 B2號(Vaartstra等人)中所描述；及其組合。The vapor phase deposition process can be used to form crystalline antimony pentoxide from a wide variety of rhodium-containing precursor compounds, including layers containing antimony pentoxide. The ruthenium-containing precursor compounds known in the art include, for example, ruthenium oxide (Ta(OMe) 5 ); ruthenium ethoxide (Ta(OEt) 5 ); ruthenium ruthenium oxide (Ta(OBu) 5 ); tantalum halide (wherein each X is independently a halogen group) of 5, such as, tantalum fluoride (TaF 5), tantalum chloride (TaCl5 5) and tantalum iodide (TAI 5); V (dimethylamino) tantalum , tris(diethylamino)(ethylimido)fluorene, tris(diethylamino)(t-butylimino)phosphonium; other ruthenium-containing precursor compounds, as in U.S. Patent No. 7,030,042 B2 (Vaartstra et al.); and combinations thereof.

在某些實施例中，可使用至少一含鉭前驅物化合物及視情況至少一反應氣體藉由氣相沈積方法形成結晶五氧化二鉭，如(例如)在美國專利第7,030,042 B2號(Vaartstra等人)中所描述。可藉由使至少一含鉭前驅物化合物與視情況在含釕材料之至少一部分上的至少一反應氣體接觸來形成此結晶五氧化二鉭。在一些實施例中，反應氣體為水蒸汽、臭氧，或其組合。In certain embodiments, at least one ruthenium-containing precursor compound and optionally at least one reactive gas may be used to form crystalline bismuth pentoxide by vapor deposition, such as, for example, in U.S. Patent No. 7,030,042 B2 (Vaartstra et al. As described in person). The crystalline antimony pentoxide can be formed by contacting at least one antimony-containing precursor compound with at least one reactive gas optionally on at least a portion of the niobium-containing material. In some embodiments, the reactive gas is water vapor, ozone, or a combination thereof.

如本文中描述之前驅物組合物可視情況實質上與一或多種反應氣體同時及在存在一或多種反應氣體之情況下經汽化及沈積/經化學吸附。或者，可藉由在每一沈積循環期間替代地引入前驅物組合物及反應氣體而形成含金屬材料。此等反應氣體可包括(例如)含氧源，其可為氧化氣體。可使用廣泛的各種各樣之合適的氧化氣體，包括(例如)氧、水蒸汽、臭氧、過氧化氫、醇(例如，異丙醇)，及其組合。As previously described herein, the precursor composition may be vaporized and deposited/chemically adsorbed substantially simultaneously with one or more reactive gases and in the presence of one or more reactive gases. Alternatively, the metal-containing material can be formed by alternatively introducing a precursor composition and a reactive gas during each deposition cycle. Such reactive gases may include, for example, an oxygen containing source, which may be an oxidizing gas. A wide variety of suitable oxidizing gases can be used including, for example, oxygen, water vapor, ozone, hydrogen peroxide, alcohols (e.g., isopropanol), and combinations thereof.

若需要，可在存在惰性載氣之情況下使前驅物組合物汽化。另外，可在ALD製程(以下論述)中之沖洗步驟中使用惰性載氣。惰性載氣通常為氮、氬、氦、氖、氪、氙、任何其他非反應性氣體，及其混合物等。在本揭示案之上下文中，惰性載氣為不干擾含金屬材料之形成的氣體。不管是否在存在惰性載氣之情況下進行，可在無氧之情況下進行汽化以避免氧污染(例如，矽之氧化以形成二氧化矽，或在進入至沈積腔室前處於汽相的前驅物之氧化)。If desired, the precursor composition can be vaporized in the presence of an inert carrier gas. Additionally, an inert carrier gas can be used in the rinsing step in the ALD process (discussed below). The inert carrier gas is typically nitrogen, argon, helium, neon, krypton, xenon, any other non-reactive gas, mixtures thereof, and the like. In the context of the present disclosure, the inert carrier gas is a gas that does not interfere with the formation of the metal-containing material. Whether or not it is carried out in the presence of an inert carrier gas, it can be vaporized without oxygen to avoid oxygen contamination (for example, oxidation of ruthenium to form ruthenium dioxide, or precursor to the vapor phase before entering the deposition chamber) Oxidation of matter).

於本文中使用時，術語「沈積製程」及「氣相沈積製程」指含金屬材料自包括一或多種含金屬化合物的汽化之前驅物組合物而形成於基板(例如，摻雜之多晶矽晶圓)之一或多個表面上的製程。具體言之，一或多種含金屬化合物經汽化且引導至及/或接觸置放於沈積腔室中的基板(例如，半導體基板或基板總成)之一或多個表面。通常，對基板加熱。此等含金屬化合物可在基板之該或該等表面上形成(例如，藉由反應或分解)非揮發性、薄的、均勻的含金屬材料。為了本揭示案之目的，術語「氣相沈積製程」意欲包括化學氣相沈積製程(包括加脈衝化學氣相沈積製程)及原子層沈積製程兩者。As used herein, the terms "deposition process" and "vapor deposition process" refer to a metal-containing material formed on a substrate from a vaporized precursor composition comprising one or more metal-containing compounds (eg, doped polysilicon wafers) a process on one or more surfaces. In particular, the one or more metal-containing compounds are vaporized and directed to and/or contact one or more surfaces of a substrate (eg, a semiconductor substrate or substrate assembly) disposed in a deposition chamber. Typically, the substrate is heated. The metal-containing compounds can form (e.g., by reacting or decomposing) a non-volatile, thin, uniform metal-containing material on the or the surface of the substrate. For the purposes of this disclosure, the term "vapor deposition process" is intended to include both chemical vapor deposition processes (including pulsed chemical vapor deposition processes) and atomic layer deposition processes.

化學氣相沈積(CVD)及原子層沈積(ALD)為常用以在半導體基板上形成薄的、連續的、均勻的含金屬材料之兩個氣相沈積製程。使用任一氣相沈積製程，通常，一或多種前驅物組合物經在沈積腔室中汽化且視情況與一或多種反應氣體組合且引導至及/或接觸基板以在基板上形成含金屬材料。熟習此項技術者將易於顯而易見，可藉由使用諸如電漿輔助、光輔助、雷射輔助以及其他技術之各種有關技術來增強氣相沈積製程。Chemical vapor deposition (CVD) and atomic layer deposition (ALD) are two vapor deposition processes commonly used to form thin, continuous, uniform metal-containing materials on semiconductor substrates. Using any vapor deposition process, typically, one or more precursor compositions are vaporized in a deposition chamber and optionally combined with one or more reactive gases and directed to and/or in contact with the substrate to form a metal-containing material on the substrate. It will be readily apparent to those skilled in the art that the vapor deposition process can be enhanced by the use of various related techniques such as plasma assisted, light assisted, laser assisted, and other techniques.

於本文中使用時，「化學氣相沈積」(CVD)指其中在沈積腔室中自汽化之含金屬化合物(及所使用之任何反應氣體)將所要層沈積於基板上而不作出分開反應組份之努力的氣相沈積製程。與涉及前驅物組合物與任何反應氣體之實質上同時使用的「簡單」CVD製程相比，「加脈衝之」CVD替代地將此等材料脈動至沈積腔室中，但不嚴格地避免如在原子層沈積或ALD(以下更詳細地論述)中通常所進行的前驅物與反應氣流之混合。As used herein, "chemical vapor deposition" (CVD) refers to a metal-containing compound (and any reactive gas used therein) that self-vaporizes in a deposition chamber to deposit a desired layer on a substrate without separate reaction groups. The vapor deposition process of the effort. In contrast to a "simple" CVD process involving the substantially simultaneous use of a precursor composition with any reactive gas, "pulsed" CVD instead pulsates these materials into the deposition chamber, but does not strictly avoid Mixing of precursors and reactive gas streams typically performed in atomic layer deposition or ALD (discussed in more detail below).

在半導體處理中，化學氣相沈積(CVD)已廣泛地用於含金屬層(諸如，介電層)之製備，此係由於其在相對快處理時間下提供保形且高品質介電層的能力。通常，在單一沈積循環中，所要前驅物組合物經汽化且接著與可選反應氣體及/或惰性載氣一起引入至含有經加熱之基板的沈積腔室內。在典型的CVD製程中，使汽化之前驅物與反應氣體在基板表面處接觸以形成材料(例如，層或介電層)。允許單一沈積循環繼續，直至達成層之所要厚度。In semiconductor processing, chemical vapor deposition (CVD) has been widely used in the preparation of metal-containing layers, such as dielectric layers, due to its ability to provide conformal and high quality dielectric layers at relatively fast processing times. ability. Typically, in a single deposition cycle, the desired precursor composition is vaporized and then introduced into a deposition chamber containing the heated substrate along with an optional reaction gas and/or an inert carrier gas. In a typical CVD process, a precursor of vaporization is contacted with a reactive gas at the surface of the substrate to form a material (eg, a layer or dielectric layer). A single deposition cycle is allowed to continue until the desired thickness of the layer is reached.

典型的CVD製程通常在汽化腔室中使用前驅物組合物，汽化腔室與沈積表面或晶圓所位於之處理腔室分開。舉例而言，液態前驅物組合物通常置放於起泡器中且經加熱至其汽化之溫度，且汽化之液態前驅物組合物接著由越過起泡器或穿過液態前驅物組合物之惰性載氣輸送。接著使蒸汽順利通過氣管至沈積腔室，用於在其中之基板表面上沈積層。已開發許多技術來精確地控制此製程。舉例而言，藉由含有前驅物組合物的儲集器之溫度及藉由使起泡之惰性載氣流過或越過儲集器，可精確地控制輸送至沈積腔室的前驅物組合物之量。A typical CVD process typically uses a precursor composition in a vaporization chamber that is separate from the deposition surface or the processing chamber in which the wafer is located. For example, the liquid precursor composition is typically placed in a bubbler and heated to a temperature at which it vaporizes, and the vaporized liquid precursor composition is then inerted by passing over the bubbler or through the liquid precursor composition. Carrier gas transport. The vapor is then passed smoothly through the gas pipe to the deposition chamber for depositing a layer on the surface of the substrate therein. Many techniques have been developed to precisely control this process. For example, the amount of precursor composition delivered to the deposition chamber can be precisely controlled by the temperature of the reservoir containing the precursor composition and by passing the bubbling inert carrier gas over or over the reservoir. .

可在化學氣相沈積反應器(諸如，在來自Genus,Inc.(Sunnyvale，CA)之商標名稱7000下可獲得之沈積腔室、在來自Applied Materials,lnc.(Santa Clara，CA)之商標名稱5000下可獲得之沈積腔室或在來自Novelus,Inc.(San Jose，CA)之商標名稱Prism下可獲得之沈積腔室)中進行典型的CVD製程。然而，可使用適合於執行CVD之任何沈積腔室。A deposition chamber available in a chemical vapor deposition reactor such as that available under the trade name 7000 from Genus, Inc. (Sunnyvale, Calif.), under the trade name from Applied Materials, lnc. (Santa Clara, CA). A typical CVD process is performed in a deposition chamber available at 5000 or in a deposition chamber available under the trade name Prism from Novelus, Inc. (San Jose, CA). However, any deposition chamber suitable for performing CVD can be used.

CVD腔室之若干修改係可能的，例如，使用常壓化學氣相沈積、低壓化學氣相沈積(LPCVD)、電漿增強型化學氣相沈積(PECVD)、熱壁或冷壁反應器或任何其他化學氣相沈積技術。此外，可使用加脈衝之CVD，其類似於ALD，但不嚴格地避免前驅物與反應氣流之混合。又，對於加脈衝之CVD，沈積厚度係視曝露時間而定，與自限制性的ALD相反(以下更詳細地論述)。Several modifications of the CVD chamber are possible, for example, using atmospheric pressure chemical vapor deposition, low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), hot wall or cold wall reactors, or any Other chemical vapor deposition techniques. In addition, pulsed CVD can be used, which is similar to ALD, but does not strictly avoid mixing of the precursor with the reactive gas stream. Again, for pulsed CVD, the thickness of the deposit depends on the exposure time, as opposed to self-limiting ALD (discussed in more detail below).

於本文中使用時，術語「原子層沈積」(ALD)指其中在處理腔室(亦即，沈積腔室)中進行沈積循環(例如，複數個連續的沈積循環)之氣相沈積製程。於本文中使用時，「複數個」意謂兩個或兩個以上。通常，在每一循環期間，使前驅物化學吸附至沈積表面(例如，基板總成表面或先前沈積之下伏表面，諸如，來自先前ALD循環之材料)，從而形成不易於與額外前驅物反應(亦即，自限制性反應)之單層或子單層。其後，若必要，可隨後將反應物(例如，另一前驅物或反應氣體)引入至處理腔室中，以供用於在沈積表面上將化學吸附之前驅物轉換為所要材料。通常，此反應物能夠與前驅物進一步反應。另外，在每一循環期間亦可利用沖洗步驟，以在經化學吸附之前驅物的轉換後自處理腔室移除過剩前驅物及/或自處理腔室移除過剩反應物及/或反應副產物。另外，於本文中使用時，當藉由前驅物組合物、反應性氣體及沖洗(例如，惰性載體)氣體之交替脈衝來執行時，術語「原子層沈積」亦意欲包括由有關術語表示之製程，諸如「化學氣相原子層沈積」、「原子層磊晶」(ALE)(例如，見頒予Ackerman之美國專利第5,256,244號)、分子束磊晶(MBE)、氣體源MBE或有機金屬MBE及化學束磊晶。As used herein, the term "atomic layer deposition" (ALD) refers to a vapor deposition process in which a deposition cycle (eg, a plurality of successive deposition cycles) is performed in a processing chamber (ie, a deposition chamber). As used herein, "plural" means two or more. Typically, during each cycle, the precursor is chemisorbed to a deposition surface (eg, a substrate assembly surface or a previously deposited underlying surface, such as a material from a previous ALD cycle) to form a precursor that is not susceptible to reaction with additional precursors. (ie, from a limiting reaction) a single layer or a sub-monolayer. Thereafter, if necessary, a reactant (e.g., another precursor or reaction gas) can then be introduced into the processing chamber for conversion of the chemisorbed precursor to the desired material on the deposited surface. Typically, this reactant is capable of reacting further with the precursor. Additionally, a rinsing step can also be utilized during each cycle to remove excess precursor from the processing chamber and/or remove excess reactants and/or reaction pairs from the processing chamber after conversion of the precursor prior to chemisorption. product. In addition, as used herein, the term "atomic layer deposition" is also intended to include a process represented by a related term when it is performed by alternating pulses of a precursor composition, a reactive gas, and a rinsing (eg, inert carrier) gas. , such as "chemical vapor atomic layer deposition", "atomic layer epitaxy" (ALE) (see, for example, U.S. Patent No. 5,256,244 to Ackerman), molecular beam epitaxy (MBE), gas source MBE or organometallic MBE And chemical beam epitaxy.

在本揭示案之一些方法中使用之氣相沈積製程可為多循環原子層沈積(ALD)製程。此製程為有利的，尤其比CVD製程有利，此在於其藉由提供複數個自限制性沈積循環而對所沈積之材料(例如，介電層)提供原子級厚度及均勻性之改良的控制。ALD之自限制性質提供一種在廣泛的各種各樣之反應表面(包括，例如，具有不規則拓撲之表面)上沈積膜之方法，其具有比藉由CVD或其他「視線」沈積方法(例如，汽化及物理氣相沈積，亦即，PVD或濺鍍)可獲得之步階覆蓋更佳的步階覆蓋。另外，ALD製程通常使含金屬化合物曝露至較低揮發及反應溫度，與(例如)典型的CVD製程相比，此傾向於減小前驅物之降級。The vapor deposition process used in some of the methods of the present disclosure may be a multi-cycle atomic layer deposition (ALD) process. This process is advantageous, especially in favor of CVD processes, in that it provides improved control of atomic thickness and uniformity of the deposited material (e.g., dielectric layer) by providing a plurality of self-limiting deposition cycles. The self-limiting nature of ALD provides a method of depositing a film on a wide variety of reactive surfaces, including, for example, surfaces having irregular topologies, having a deposition method by CVD or other "line of sight" (eg, Vaporization and physical vapor deposition, that is, PVD or sputtering, can achieve a step coverage with better coverage. In addition, ALD processes typically expose metal-containing compounds to lower volatility and reaction temperatures, which tend to reduce degradation of precursors compared to, for example, typical CVD processes.

通常，在ALD製程中，通常在至少25℃，在某些實施例中，至少150℃，且在其他實施例中，至少200℃之沈積溫度下將每一反應物脈動至合適的基板上。典型的ALD沈積溫度小於或等於400℃，在某些實施例中，小於或等於350℃，且在其他實施例中，小於或等於250℃。此等溫度通常低於當前在CVD製程中使用之溫度，在CVD製程中使用之溫度通常包括至少150℃的在基板表面處之沈積溫度，在一些實施例中，至少200℃，且在其他實施例中，至少250℃。在多數實施例中，CLD沈積溫度小於或等於500℃，在某些實施例中，小於或等於450℃，且在其他實施例中，小於或等於400℃。Typically, each reactant is pulsed onto a suitable substrate in an ALD process, typically at least 25 ° C, in some embodiments, at least 150 ° C, and in other embodiments, at a deposition temperature of at least 200 ° C. Typical ALD deposition temperatures are less than or equal to 400 °C, in certain embodiments, less than or equal to 350 °C, and in other embodiments, less than or equal to 250 °C. These temperatures are typically lower than those currently used in CVD processes, and the temperatures used in the CVD process typically include a deposition temperature at the substrate surface of at least 150 ° C, in some embodiments, at least 200 ° C, and in other implementations. In the case, at least 250 ° C. In most embodiments, the CLD deposition temperature is less than or equal to 500 °C, in some embodiments, less than or equal to 450 °C, and in other embodiments, less than or equal to 400 °C.

典型的ALD製程包括將基板(視情況，可藉由(例如)水及/或臭氧來預處理該基板)曝露至第一化學品以實現化學品至基板之化學吸附。於本文中使用時，術語「化學吸附」指經汽化之反應性含金屬化合物在基板之表面上的化學吸附。作為以高吸附能量(例如，>30 kcal/mol)為特徵之相對強的鍵結力(在強度上與普通化學鍵相當)之結果，所吸附之化學品通常不可逆地鍵結至基板表面。經化學吸附之化學品通常在基板表面上形成單層。(見，例如，由G.G.Hawley修訂，由紐約的Van Nostrand Reinhold Co.出版之「The Condensed Chemical Dictionary」第10版，225(1981))。在ALD中，將一或多種適當的前驅物組合物或反應氣體交替地引入(例如，加脈衝)至沈積腔室內，且化學吸附至基板之表面上。反應性化合物之每一順序引入(例如，一或多種前驅物組合物及一或多種反應氣體)通常由惰性載氣沖洗分開，以在實質上無第一反應性化合物之情況下提供第二反應性化合物之沈積及/或化學吸附。於本文中使用時，在第二反應性化合物之沈積及/或化學吸附期間的第一反應性化合物之「實質上不存在」意謂可存在不大於可忽略量的第一反應性化合物。根據一般熟習此項技術者之知識，可進行關於第一反應性化合物之容許量之判定，且可選擇製程條件以達成第一反應性化合物之實質上不存在。A typical ALD process involves exposing a substrate (which may be pretreated by, for example, water and/or ozone, as appropriate) to a first chemical to effect chemical adsorption of the chemical to the substrate. As used herein, the term "chemical adsorption" refers to the chemisorption of a vaporized reactive metal-containing compound on the surface of a substrate. As a result of the relatively strong bonding force (which is equivalent in strength to ordinary chemical bonds) characterized by high adsorption energy (eg, >30 kcal/mol), the adsorbed chemical is typically irreversibly bonded to the substrate surface. Chemically adsorbed chemicals typically form a single layer on the surface of the substrate. (See, for example, Revised by G. G. Hawley, "The Condensed Chemical Dictionary," 10th edition, 225 (1981), published by Van Nostrand Reinhold Co., New York. In ALD, one or more suitable precursor compositions or reaction gases are introduced (eg, pulsed) into the deposition chamber alternately and chemically adsorbed onto the surface of the substrate. Each sequence of reactive compounds introduced (eg, one or more precursor compositions and one or more reactive gases) is typically separated by an inert carrier gas purge to provide a second reaction in the substantial absence of the first reactive compound. Deposition and/or chemisorption of a compound. As used herein, "substantially absent" of a first reactive compound during deposition and/or chemisorption of a second reactive compound means that no more than a negligible amount of the first reactive compound may be present. The determination of the tolerance for the first reactive compound can be made based on the knowledge of those of ordinary skill in the art, and the process conditions can be selected to achieve substantial absence of the first reactive compound.

每一前驅物組合物共反應將新的原子層添加至先前沈積之層以形成累積的固體。重複該循環以逐漸形成所要厚度。應理解，ALD可交替地利用一經化學吸附之前驅物組合物及一與經化學吸附之前驅物組合物反應之反應氣體。Each precursor composition co-reacts to add a new atomic layer to the previously deposited layer to form a cumulative solid. This cycle is repeated to gradually form the desired thickness. It will be appreciated that ALD may alternatively utilize a chemisorbed precursor composition and a reactive gas that reacts with the chemisorbed precursor composition.

典型的ALD製程包括將初始基板曝露至第一化學品A(例如，諸如如本文中描述之含金屬化合物之前驅物組合物或反應氣體)以實現化學品A至基板上之化學吸附。化學品A可與基板表面或與化學器B(以下描述)反應，但自身不反應。當化學品A為具有配位體之含金屬化合物時，在化學吸附期間，配位體中之一或多者通常由反應性基團移位於基板表面上。理論上，化學吸附形成在整個曝露之初始基板上為均勻的一原子或分子厚之單層，該單層由化學品A、極少量的移位之配位體構成。換言之，飽和單層實質上形成於基板表面上。A typical ALD process involves exposing an initial substrate to a first chemical A (eg, a metal-containing compound precursor composition or a reactive gas such as described herein) to effect chemical adsorption of chemical A onto the substrate. Chemical A can react with the surface of the substrate or with chemical B (described below) but does not react by itself. When the chemical A is a metal-containing compound having a ligand, one or more of the ligands are usually moved from the reactive group on the surface of the substrate during chemisorption. Theoretically, chemisorption forms a single layer of one atom or molecular thickness that is uniform over the entire exposed substrate. The monolayer consists of a chemical A, a very small amount of displaced ligand. In other words, the saturated monolayer is formed substantially on the surface of the substrate.

化學品A以及移位之配位體的實質上所有未化學吸附之分子經自基板上沖洗，且提供第二化學品-化學品B(例如，不同的含金屬化合物或反應氣體)以與化學品A之單層反應。化學品B通常自化學品A單層移位剩餘的配位體，且藉此經化學吸附且形成第二單層。此第二單層顯示僅對化學品A有反應性之表面。未化學吸附之化學品B以及經移位之配位體及其他反應副產物接著經沖洗，且重複該等步驟，其中將化學品B單層曝露至汽化之化學品A。視情況，化學品B可與化學品A反應，但不將額外材料化學吸附至其處。亦即，化學品B可分解經化學吸附之化學品A的某部分，從而更改此單層，而不在其上形成另一單層’但使反應性部位可用於隨後單層之形成。在其他ALD製程中，可如同對於化學品A及化學品B所描述來連續地化學吸附(或反應)及沖洗第三或更多的化學品，應理解，每一引入之化學品與緊接在其引入前生成之單層反應。視情況，化學品B(或第三或隨後的化學品)可包括至少一反應氣體(若需要)。Substantially all of the chemisorbed molecules of the chemical A and the displaced ligand are washed from the substrate and provide a second chemical - chemical B (eg, a different metal containing compound or reactive gas) to chemistry A single layer reaction of product A. Chemical B typically shifts the remaining ligand from the chemical A monolayer and thereby chemically adsorbs and forms a second monolayer. This second monolayer shows a surface that is only reactive to Chemical A. The chemisorbed chemical B and the displaced ligand and other reaction by-products are then rinsed and the steps repeated, wherein the chemical B monolayer is exposed to the vaporized chemical A. Chemical B can react with Chemical A, as appropriate, but does not chemically adsorb additional materials to it. That is, the chemical B can decompose a portion of the chemically adsorbed chemical A, thereby modifying the monolayer without forming another monolayer thereon' but making the reactive site available for subsequent formation of a single layer. In other ALD processes, the third or more chemicals can be continuously chemisorbed (or reacted) and flushed as described for Chemicals A and B. It should be understood that each introduced chemical is immediately followed. A monolayer reaction that is generated prior to its introduction. Chemical B (or a third or subsequent chemical) may include at least one reactive gas (if desired), as appropriate.

實務上，化學吸附可不發生於沈積表面之所有部分(例如，先前沈積之ALD材料)上。然而，此不完美之單層在本揭示案之上下文中仍看作單層。在許多應用中，僅實質上飽和單層可為合適的。在一態樣中，實質上飽和單層為將仍產生展現出所要品質及/或特性的沈積之單層或較少材料之單層。在另一態樣中，實質上飽和單層為自限制與前驅物進一步反應之單層。In practice, chemisorption may not occur on all parts of the deposition surface (eg, previously deposited ALD materials). However, this imperfect monolayer is still considered a single layer in the context of this disclosure. In many applications, only a substantially saturated monolayer may be suitable. In one aspect, the substantially saturated monolayer is a single layer that will still produce a single layer or less of material that exhibits the desired quality and/or properties. In another aspect, the substantially saturated monolayer is a monolayer that is self-limiting and further reacts with the precursor.

藉由ALD進行之膜生長通常為自限制性的(亦即，當在ALD製程中耗盡了表面上之反應性部位時，沈積通常停止)，此可提供在晶圓內之實質上沈積一致性及沈積厚度控制。歸因於前驅物組合物及/或反應氣體之交替配料，與藉由前驅物及/或反應氣體之連續共反應進行之CVD製程相比，有害的蒸汽相反應固有地減少。(見，例如，Vehkamki等人之「Growth of SrTiO3 and BaTiO3 Thin Films by Atomic Layer Deposition」(Electrochemical and Solid-State Letters，2(10)：504-506(1999)))。Film growth by ALD is typically self-limiting (i.e., when the reactive sites on the surface are depleted in the ALD process, the deposition typically stops), which provides substantially uniform deposition within the wafer. Sex and sediment thickness control. Due to the alternating dosing of the precursor composition and/or the reactive gas, the detrimental vapor phase reaction is inherently reduced compared to the CVD process by continuous co-reaction of the precursor and/or reactive gas. (See, for example, Vehmam Ki et al., "Growth of SrTiO 3 and BaTiO 3 Thin Films by Atomic Layer Deposition" (Electrochemical and Solid-State Letters, 2 (10): 504-506 (1999)).

ALD常被描述為自限制性製程，其在於在第一化學品可形成至其的化學鍵之基板上存在有限數目個反應部位。第二化學品可僅與自第一化學品之化學吸附產生之表面反應，且因此，亦可為自限制性的。一旦基板上之所有的有限數目個反應性部位與第一化學品鍵結，則該第一化學品將不鍵結至已與基板鍵結的第一化學品中之其他者。然而，在ALD中可變化製程條件以促進此鍵結且致使ALD為非自限制性的，例如，更類似於加脈衝之CVD。因此，ALD亦可包含藉由化學品之堆疊，化學品一次形成不同於一個之單層，從而形成一個以上原子或分子厚之材料。ALD is often described as a self-limiting process in that there is a finite number of reaction sites on a substrate to which the first chemical can form a chemical bond. The second chemical may only react with the surface produced by chemisorption of the first chemical and, therefore, may also be self-limiting. Once all of the limited number of reactive sites on the substrate are bonded to the first chemical, the first chemical will not bond to the other of the first chemicals that have been bonded to the substrate. However, process conditions can be varied in ALD to facilitate this bonding and render ALD non-self-limiting, for example, more similar to pulsed CVD. Thus, ALD can also include the formation of a single layer of one or more atoms or molecules thick by chemically forming a single layer different from one by chemical stacking.

因此，在ALD製程期間，可在沈積腔室中進行眾多連續的沈積循環，每一循環沈積很薄的含金屬層(通常，少於一個之單層，使得生長速率平均為每循環0.02至0.3奈米)，直至在相關基板上建置起所要厚度之材料。藉由將前驅物組合物交替地引入(亦即，藉由加脈衝)至含有基板之沈積腔室中、將作為單層之前驅物組合物化學吸附至基板表面上、沖洗沈積腔室、接著在複數個沈積循環中引入至經化學吸附之前驅物組合物反應氣體及/或其他前驅物組合物直至達成含金屬材料之所要厚度，可實現沈積。Thus, during the ALD process, numerous successive deposition cycles can be performed in the deposition chamber, each layer depositing a very thin metal-containing layer (typically, less than a single layer, resulting in an average growth rate of 0.02 to 0.3 per cycle) Nano) until the material of the desired thickness is built on the relevant substrate. By chemically adsorbing the precursor composition into the deposition chamber containing the substrate, by chemically adsorbing the precursor composition to the substrate surface, rinsing the deposition chamber, and then rinsing the deposition chamber, Deposition can be achieved by introducing a chemically adsorbed precursor composition reaction gas and/or other precursor composition into a plurality of deposition cycles until a desired thickness of the metal-containing material is achieved.

因此，ALD之使用通常提供改良基板上的含金屬材料之厚度、組合物及均勻性之控制的能力。舉例而言，在複數個循環中沈積含金屬化合物之薄層提供最終膜厚度之更準確控制。當前驅物組合物經引導至基板且允許化學吸附於其上時，此特別有利(視情況，進一步包括可與基板上之經化學吸附之前驅物組合物反應之至少一反應氣體，且在某些實施例中，其中此循環經重複至少一次)。Thus, the use of ALD typically provides the ability to improve the control of the thickness, composition, and uniformity of the metal-containing material on the substrate. For example, depositing a thin layer of a metal-containing compound in a plurality of cycles provides a more accurate control of the final film thickness. This is particularly advantageous when the precursor composition is directed to the substrate and allows chemisorption thereon (including, where appropriate, at least one reactive gas that can react with the chemically adsorbed precursor composition on the substrate, and at some In some embodiments, wherein the cycle is repeated at least once).

在至基板上之沈積及/或化學吸附後的每一化學品之過剩蒸汽之沖洗可包含各種各樣之技術，包括(但不限於)使基板及/或單層與惰性載氣接觸及/或將壓力降低至低於沈積壓力以減小接觸基板的化學品及/或化學吸附之化學品之濃度。如上論述的惰性載氣之實例可包括氮、氬、氦等。另外，沖洗可替代地包括使基板及/或單層與允許化學吸附副產物解吸附及減小在引入另一化學品之前的接觸化學品之濃度之任何物質接觸。可基於特定沈積製程之產物的規格將接觸化學品減小至熟習此項技術者已知之某一合適的濃度或部分壓力。Flushing of excess vapor of each chemical after deposition onto the substrate and/or chemisorption may include a variety of techniques including, but not limited to, contacting the substrate and/or monolayer with an inert carrier gas and/or Or lowering the pressure below the deposition pressure to reduce the concentration of chemicals and/or chemisorbed chemicals that contact the substrate. Examples of the inert carrier gas as discussed above may include nitrogen, argon, helium, and the like. Additionally, rinsing may alternatively include contacting the substrate and/or the monolayer with any material that allows the chemisorbed byproduct to desorb and reduce the concentration of the contact chemical prior to introduction of another chemical. The contact chemical can be reduced to a suitable concentration or partial pressure known to those skilled in the art based on the specifications of the product of the particular deposition process.

前驅物組合物及惰性載氣之脈衝持續時間通常具有足夠使基板表面飽和之持續時間。通常，脈衝持續時間為至少0.1秒，在某些實施例中，至少0.2秒，且在其他實施例中，至少0.5秒。通常，脈衝持續時間通常小於或等於2分鐘，且在某些實施例中，小於或等於1分鐘。The pulse duration of the precursor composition and the inert carrier gas typically has a duration sufficient to saturate the surface of the substrate. Typically, the pulse duration is at least 0.1 seconds, in some embodiments, at least 0.2 seconds, and in other embodiments, at least 0.5 seconds. Typically, the pulse duration is typically less than or equal to 2 minutes, and in some embodiments, less than or equal to 1 minute.

與主要為熱驅動之CVD相比，ALD主要為化學驅動。因此，可在比CVD低得多之溫度下有利地進行ALD。在ALD製程期間，可將基板溫度維持於足夠低以維持化學吸附之化學品與下伏基板表面之間的完整鍵結且防止化學品(例如，前驅物組合物)之分解的溫度下。另一方面，溫度必須足夠高以避免化學品(例如，前驅物組合物)之縮合。通常，使基板保持於至少25℃之溫度下，在某些實施例中，至少150℃，且在一些實施例中，至少200℃。通常，使基板保持於小於或等於400℃之溫度下，在某些實施例中，小於或等於350℃，且在某些其他實施例中，小於或等於300℃，如上所論述，該溫度通常比當前在典型CVD製程中使用之溫度低。可在第一溫度下化學吸附第一化學品或前驅物組合物，且可在實質上相同溫度下(或視情況，在實質上不同溫度下)發生第二化學品或前驅物組合物之表面反應。顯而易見，如由一般熟習此項技術者判斷的溫度之一些小變化可發生，但藉由提供統計上與在第一化學品或前驅物化學吸附之溫度下將發生的相同的反應速率，其仍可被看作實質上相同溫度。或者，化學吸附及隨後的反應可替代地發生於實質上完全相同的溫度下。ALD is primarily chemically driven compared to CVD, which is primarily thermally driven. Therefore, ALD can be advantageously performed at a temperature much lower than CVD. During the ALD process, the substrate temperature can be maintained at a temperature low enough to maintain complete bonding between the chemisorbed chemical and the underlying substrate surface and to prevent decomposition of chemicals (eg, precursor compositions). On the other hand, the temperature must be high enough to avoid condensation of chemicals (eg, precursor compositions). Typically, the substrate is maintained at a temperature of at least 25 ° C, in certain embodiments, at least 150 ° C, and in some embodiments, at least 200 ° C. Typically, the substrate is maintained at a temperature less than or equal to 400 ° C, in some embodiments, less than or equal to 350 ° C, and in certain other embodiments, less than or equal to 300 ° C, as discussed above, typically It is lower than the temperature currently used in typical CVD processes. The first chemical or precursor composition can be chemisorbed at a first temperature, and the surface of the second chemical or precursor composition can occur at substantially the same temperature (or, as the case may be, at substantially different temperatures) reaction. It will be apparent that some small changes in temperature as judged by those skilled in the art can occur, but by providing the same rate of reaction that would occur statistically at the temperature of the chemisorption of the first chemical or precursor, Can be considered as substantially the same temperature. Alternatively, chemisorption and subsequent reactions may alternatively occur at substantially the same temperature.

對於典型的氣相沈積製程，沈積腔室內部之壓力可為至少10-8 托(torr)(1.3×10-6 帕斯卡「Pa」)，在某些實施例中，至少10-7 托(1.3×10-5 Pa)，且在某些其他實施例中，至少10-6 托(1.3×10-4 Pa)。另外，沈積壓力通常小於或等於20托(2.7×103 Pa)，在某些實施例中，小於或等於5托(6.7×102 Pa)，且在某些其他實施例中，小於或等於2托(2.7×102 Pa)。通常，在於每一循環中經汽化之前驅物組合物已經引入至腔室內及/或反應後，用惰性載氣沖洗沈積腔室。在每一循環期間，該或該等惰性載氣亦可與經汽化之前驅物組合物一起引入。For a typical vapor deposition process, the pressure inside the deposition chamber can be at least 10 -8 torr (1.3 x 10 -6 Pascal "Pa"), and in some embodiments, at least 10 -7 torr (1.3 ×10 -5 Pa), and in certain other embodiments, at least 10 -6 Torr (1.3 x 10 -4 Pa). Additionally, the deposition pressure is typically less than or equal to 20 Torr (2.7 x 10 3 Pa), in some embodiments, less than or equal to 5 Torr (6.7 x 10 2 Pa), and in certain other embodiments, less than or equal to 2 Torr (2.7 × 10 2 Pa). Typically, the deposition chamber is flushed with an inert carrier gas after the vaporized composition has been introduced into the chamber and/or after the vaporization in each cycle. The or the inert carrier gas may also be introduced with the vaporized precursor composition during each cycle.

前驅物組合物之反應性可顯著地影響ALD中之製程參數。在典型的CVD製程條件下，高反應性化學品(例如，高反應性前驅物組合物)可在氣相中反應，從而產生微粒，過早地沈積於不當的表面上，生成不適當之膜及/或不適當之步階覆蓋，或另外產生不均勻沈積。因為至少此原因，可認為高反應性化學品不適合於CVD。然而，不適合於CVD之一些化學品在用於ALD之前驅物組合物中係極佳的。舉例而言，若第一化學品為與第二化學品反應之氣相，則化學品之此組合可能不適合於CVD，但其可用於ALD中。在CVD環境中，當使用高氣相反應性化學品時，亦可能存在關於黏著係數及表面遷移率之關注，如熟習此項技術者已知，然而，在ALD環境中將幾乎不存在或不存在此關注。The reactivity of the precursor composition can significantly affect process parameters in ALD. Under typical CVD process conditions, highly reactive chemicals (eg, highly reactive precursor compositions) can react in the gas phase to produce microparticles that prematurely deposit on improper surfaces, creating an inappropriate film. And/or inappropriate step coverage, or otherwise uneven deposition. For at least this reason, highly reactive chemicals are considered to be unsuitable for CVD. However, some chemicals that are not suitable for CVD are excellent in the precursor composition for ALD. For example, if the first chemical is in the gas phase that reacts with the second chemical, this combination of chemicals may not be suitable for CVD, but it can be used in ALD. In CVD environments, when high gas phase reactive chemicals are used, there may also be concerns about adhesion coefficients and surface mobility, as is known to those skilled in the art, however, there will be little or no in an ALD environment. There is this concern.

本揭示案之形成氧化物(例如，五氧化二鉭)及物品之方法可對於半導體結構中之廣泛的各種各樣之薄膜應用(特別地，使用高介電係數材料之薄膜應用)有益。舉例而言，此等應用包括閘極介電及電容器，諸如，平坦單元、溝渠單元(例如，雙側壁溝渠電容器)、堆疊之單元(例如，冠狀、V形單元、三角形單元、多指狀或圓柱形容器堆疊之電容器)，以及場效電晶體器件。The methods of forming oxides (e.g., antimony pentoxide) and articles of the present disclosure can be beneficial for a wide variety of film applications in semiconductor structures, particularly film applications using high dielectric material. For example, such applications include gate dielectrics and capacitors, such as flat cells, trench cells (eg, double sidewall trench capacitors), stacked cells (eg, crowns, V-shaped cells, triangular cells, multi-finger or Capacitors stacked in cylindrical containers), and field effect transistor devices.

圖2說明物品110，其具有一電極130(例如，含釕材料)、在電極130之至少一部分上且具有第一結晶取向之第一結晶五氧化二鉭140，及在第一結晶五氧化二鉭140之至少一部分上、具有第二結晶取向之第二結晶五氧化二鉭150。物品110視情況包括在第二結晶五氧化二鉭150上之第二電極(未圖示)。2 illustrates an article 110 having an electrode 130 (eg, a germanium-containing material), a first crystalline tantalum pentoxide 140 having a first crystalline orientation on at least a portion of the electrode 130, and a first crystalline pentoxide A second crystalline bismuth pentoxide 150 having a second crystal orientation is formed on at least a portion of the crucible 140. The article 110 optionally includes a second electrode (not shown) on the second crystalline bismuth pentoxide 150.

含釕材料30、電極130、結晶五氧化二鉭40及第一結晶五氧化二鉭140及第二結晶五氧化二鉭150經描繪為具有均勻厚度。雖然此等材料(例如，含釕材料及/或五氧化二鉭)可具有實質上均勻厚度，但本揭示案中之材料可具有不均勻厚度。舉例而言，一些含釕材料30或電極130可含有拓撲特徵(例如，通道、溝渠等)(未圖示)。結晶五氧化二鉭40及第一結晶五氧化二鉭140可分別形成於具有激進拓撲之此含釕材料30或電極130上，且可填充於此等拓撲特徵中。The cerium-containing material 30, the electrode 130, the crystalline bismuth pentoxide 40 and the first crystalline bismuth pentoxide 140 and the second crystalline bismuth pentoxide 150 are depicted as having a uniform thickness. While such materials (eg, niobium-containing materials and/or tantalum pentoxide) may have a substantially uniform thickness, the materials in the present disclosure may have a non-uniform thickness. For example, some of the germanium containing material 30 or electrode 130 may contain topological features (eg, channels, trenches, etc.) (not shown). The crystalline antimony pentoxide 40 and the first crystalline antimony pentoxide 140 can be formed on the tantalum-containing material 30 or electrode 130 having a radical topology, respectively, and can be filled in such topological features.

在一些實施例中，可將一或多個中間物或***材料安置於(例如)含釕材料30與第一五氧化二鉭40之間，或圖2中描繪之材料之間(例如，電極130與第一結晶五氧化二鉭140之間或第一結晶五氧化二鉭140與第二結晶五氧化二鉭150之間)。圖1、圖2及圖3未按比例繪製，且不應藉此受到限制。舉例而言，圖1及圖2中的材料(例如，含釕材料及五氧化二鉭)之厚度可相同或不同，其不受限制。In some embodiments, one or more intermediates or intervening materials may be disposed between, for example, the ruthenium containing material 30 and the first tantalum pentoxide 40, or between the materials depicted in FIG. 2 (eg, an electrode) 130 is between the first crystalline antimony pentoxide 140 or between the first crystalline antimony pentoxide 140 and the second crystalline antimony pentoxide 150). 1, 2 and 3 are not drawn to scale and should not be limited thereby. For example, the thickness of the materials in FIGS. 1 and 2 (eg, bismuth-containing material and tantalum pentoxide) may be the same or different, and is not limited.

圖3展示如在一實例電容器構造中使用的本揭示案之含金屬層之ALD形成之一實例。參看圖3，電容器構造200包括基板210，基板210具有形成於其中之導電擴散區215。基板210可包括(例如)矽。諸如BPSG之絕緣材料260提供於基板210上，其中在其中將接觸開口280提供至擴散區215。導電材料290填充接觸開口280，且可包括(例如)鎢或導電摻雜之多晶矽。電容器構造200包括作為第一電極(底部電極)220的含釕材料、可藉由如本文中描述之方法形成之五氧化二鉭介電材料240，及第二電容器電極(頂部電極)250。五氧化二鉭介電材料240可如本文中所描述形成於第一電極220之含釕材料之至少一部分上。形成於結晶五氧化二鉭介電材料240之至少一部分上的第二電容器電極250可視情況包括釕金屬。3 shows an example of ALD formation of a metal-containing layer of the present disclosure as used in an example capacitor construction. Referring to FIG. 3, capacitor construction 200 includes a substrate 210 having a conductive diffusion region 215 formed therein. Substrate 210 can include, for example, germanium. An insulating material 260 such as BPSG is provided on the substrate 210, wherein the contact opening 280 is provided to the diffusion region 215 therein. Conductive material 290 fills contact opening 280 and may include, for example, tungsten or a conductive doped polysilicon. The capacitor construction 200 includes a germanium-containing material as a first electrode (bottom electrode) 220, a tantalum pentoxide dielectric material 240 that can be formed by a method as described herein, and a second capacitor electrode (top electrode) 250. The tantalum pentoxide dielectric material 240 can be formed on at least a portion of the tantalum-containing material of the first electrode 220 as described herein. The second capacitor electrode 250 formed on at least a portion of the crystalline tantalum pentoxide dielectric material 240 may optionally include a base metal.

圖1至圖3描繪可用於在如本文中描述之任何基板(例如，半導體結構)上形成材料之實例構造及方法，且此等應用包括(但不限於)諸如平坦單元、溝渠單元(例如，雙側壁溝渠電容器)、堆疊之單元(例如，冠狀、V形單元、三角形單元、多指狀或圓柱形容器堆疊之電容器)之電容器以及場效電晶體器件。1 through 3 depict example configurations and methods that can be used to form materials on any of the substrates (eg, semiconductor structures) as described herein, and such applications include, but are not limited to, such as flat cells, trench cells (eg, Double-sided trench capacitors, capacitors of stacked cells (eg, crowns, V-shaped cells, triangular cells, multi-finger or cylindrical container stacked capacitors) and field effect transistor devices.

此外，擴散障壁材料(未圖示)可視情況形成於五氧化二鉭介電材料240上，且可(例如)包括TiN、TaN、金屬矽化物或金屬矽化物-氮化物。雖然將擴散障壁材料描述為不同的材料，但障壁材料可包括導電材料，且可因此在此等實施例中包括電容器電極之至少一部分。在包括擴散障壁材料之某些實施例中，整個電容器電極可包括導電障壁材料。In addition, a diffusion barrier material (not shown) may optionally be formed on the tantalum pentoxide dielectric material 240 and may, for example, comprise TiN, TaN, metal telluride or metal telluride-nitride. While the diffusion barrier material is described as a different material, the barrier material can include a conductive material, and thus can include at least a portion of the capacitor electrode in such embodiments. In certain embodiments including a diffusion barrier material, the entire capacitor electrode can comprise a conductive barrier material.

實例Instance

實例1：在電腦控制下將具有與其耦接在一起之水蒸汽產生器之沈積腔室設置氣動閥以按順次方式脈衝打開閥。連接至腔室之三個儲集器含有氫、氧及氟化鉭(TaF5 )。基板為具有元素釕之頂層的二氧化矽，且維持於400℃下用於結晶五氧化二鉭之沈積。Example 1: A pneumatic valve is provided in a deposition chamber having a water vapor generator coupled thereto under computer control to pulse open the valve in a sequential manner. The three reservoirs connected to the chamber contain hydrogen, oxygen and barium fluoride (TaF 5 ). The substrate was ruthenium dioxide having a top layer of elemental ruthenium and was maintained at 400 ° C for the deposition of crystalline bismuth pentoxide.

以6：3之氫對氧原子比(90 sccm(每分鐘標準立方公分)之氫及45 sccm之氧)將氫及氧饋入至水蒸汽產生器。接著將氟化鉭及來自水蒸汽產生器之出口流交替地脈動至沈積腔室內以形成結晶五氧化二鉭。每一循環涉及氟化鉭之5秒脈衝及水蒸汽產生器出口流之5秒脈衝。使用設定於100 sccm下之質量流量控制器將鉭前驅物及水蒸汽產生器出口流與氦載氣一起引入。在100次循環後，獲得100厚之五氧化二鉭膜。五氧化二鉭之隨後的低掠角入射x射線繞射(GIXRD)掃描揭露等於約23度((003)取向)的在2θ下之主峰值及等於約46度((006)取向)的在2θ下之較小峰值，藉此指示c軸結晶組構之五氧化二鉭。Hydrogen and oxygen are fed to the steam generator at a hydrogen to oxygen ratio of 6:3 (90 sccm (standard cubic centimeters per minute) of hydrogen and 45 sccm of oxygen). The cesium fluoride and the outlet stream from the water vapor generator are then alternately pulsed into the deposition chamber to form crystalline bismuth pentoxide. Each cycle involves a 5 second pulse of cesium fluoride and a 5 second pulse of the steam generator exit stream. The helium precursor and water vapor generator outlet streams were introduced with helium carrier gas using a mass flow controller set at 100 sccm. After 100 cycles, get 100 Thick pentoxide film. Subsequent low-grazing angle incident x-ray diffraction (GIXRD) scan of tantalum pentoxide reveals a main peak at 2θ equal to about 23 degrees ((003) orientation) and equal to about 46 degrees ((006) orientation) A smaller peak at 2θ, thereby indicating the pentoxide pentoxide of the c-axis crystal structure.

實例2：與實例1相同，除了將氫對氧比率改變至8：3之外。五氧化二鉭之GIXRD掃描揭露等於約28度((200)取向)的在2θ下之主峰值及等於約50度((220)取向)及56度((102)取向)的在2θ下之較小峰值，藉此指示具有主a軸取向之五氧化二鉭。Example 2: Same as Example 1, except that the hydrogen to oxygen ratio was changed to 8:3. The GIXRD scan of antimony pentoxide reveals a main peak at 2θ equal to about 28 degrees ((200) orientation) and a ratio of about 50 degrees ((220) orientation) and 56 degrees ((102) orientation) at 2θ. A smaller peak, thereby indicating the bismuth pentoxide having a primary a-axis orientation.

本文中引用之專利、專利文獻及公開案之全部揭示內容以引用方式全部併入，如同每一者經個別地併入。在不脫離本揭示案之範疇及精神的情況下，對本文中描述之實施例之各種修改及變更對熟習此項技術者而言將變得顯而易見。應理解，本揭示案並不意欲不適當地受限於本文所闡明之說明性實施例及實例，且此等實例及實施例係僅在本揭示案之範疇內作為實例而呈現，本揭示案之範疇意欲僅受限於本文如下闡明之申請專利範圍。於本文中使用時，術語「包含」(其與「包括」或「含有」同義)係包括性的、開端式的，且不排除額外的未列舉之要素或方法步驟。The entire disclosures of the patents, patent documents and publications cited herein are hereby incorporated by reference in their entirety in their entirety herein Various modifications and alterations to the embodiments described herein will become apparent to those skilled in the art. It should be understood that the present disclosure is not intended to be limited to the illustrative embodiments and examples set forth herein, and such examples and embodiments are presented by way of example only in the scope of the present disclosure. The scope of the invention is intended to be limited only by the scope of the patent application as set forth below. As used herein, the term "comprising" (which is synonymous with "including" or "comprising") is intended to be inclusive, and does not exclude additional unrecited elements or method steps.

10．．．構造10. . . structure

30．．．含釕材料30. . . Antimony material

40．．．結晶五氧化二鉭40. . . Crystalline antimony pentoxide

110．．．物品110. . . article

130．．．電極130. . . electrode

140．．．第一結晶五氧化二鉭140. . . First crystalline antimony pentoxide

150．．．第二結晶五氧化二鉭150. . . Second crystalline bismuth pentoxide

200．．．電容器構造200. . . Capacitor construction

210．．．基板210. . . Substrate

215．．．導電擴散區215. . . Conductive diffusion zone

220．．．第一電極(底部電極)220. . . First electrode (bottom electrode)

240．．．五氧化二鉭介電材料240. . . Bismuth pentoxide dielectric material

250．．．第二電容器電極(頂部電極)250. . . Second capacitor electrode (top electrode)

260．．．絕緣材料260. . . Insulation Materials

280．．．接觸開口280. . . Contact opening

290．．．導電材料290. . . Conductive material

圖1為說明如本揭示案中進一步描述的在含釕材料之至少一部分上具有五氧化二鉭的構造之一實施例之示意性側視圖。1 is a schematic side view illustrating one embodiment of a configuration having tantalum pentoxide on at least a portion of a niobium containing material as further described in the present disclosure.

圖2為說明如本揭示案中進一步描述的在含釕材料之至少一部分上具有兩種五氧化二鉭(該等五氧化二鉭具有不同的結晶取向)的構造之一實施例之示意性側視圖。2 is a schematic side view showing one embodiment of a configuration having two bismuth pentoxides (the bismuth pentoxide having different crystal orientations) on at least a portion of the cerium-containing material as further described in the present disclosure. view.

圖3為說明如本揭示案中進一步描述的在含釕電極之至少一部分上具有五氧化二鉭(例如，五氧化二鉭介電材料或層)的一實例電容器構造之示意性側視圖。3 is a schematic side view illustrating an example capacitor configuration having tantalum pentoxide (eg, a tantalum pentoxide dielectric material or layer) on at least a portion of a germanium containing electrode as further described in the present disclosure.

如本文中描述的物品及方法之各種實施例之以上描述並不意欲描述此等方法之每一實施例或每個實施。實情為，藉由參照考慮到附圖之以下描述及申請專利範圍，將顯見且瞭解如本文中描述的方法之更完整理解。另外，應理解，在不脫離本揭示案之範疇的情況下，可利用其他實施例，且可進行結構改變。The above description of various embodiments of the articles and methods described herein is not intended to describe each or every embodiment of such methods. Rather, a more complete understanding of the method as described herein will be apparent and In addition, it is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the disclosure.

200．．．電容器構造200. . . Capacitor construction

210．．．基板210. . . Substrate

215．．．導電擴散區215. . . Conductive diffusion zone

220．．．第一電極(底部電極)220. . . First electrode (bottom electrode)

240．．．五氧化二鉭介電材料240. . . Bismuth pentoxide dielectric material

250．．．第二電容器電極(頂部電極)250. . . Second capacitor electrode (top electrode)

260．．．絕緣材料260. . . Insulation Materials

280．．．接觸開口280. . . Contact opening

290．．．導電材料290. . . Conductive material

Claims (27)

一種形成一氧化物之方法，其包含：使一含釕材料與一包含一含鉭前驅物之第一蒸汽接觸；提供一包含一或多個入口流及一出口流之水蒸汽產生器，其中該出口流包含水；及使該含釕材料與該出口流在於該含釕材料上形成結晶五氧化二鉭之條件下接觸。 A method of forming an oxide comprising: contacting a ruthenium-containing material with a first vapor comprising a ruthenium-containing precursor; providing a water vapor generator comprising one or more inlet streams and an outlet stream, wherein The outlet stream comprises water; and contacting the cerium-containing material with the outlet stream under conditions that form crystalline bismuth pentoxide on the cerium-containing material. 如請求項1之方法，其中該出口流進一步包含氫分子(H2 )。The method of claim 1, wherein the outlet stream further comprises a hydrogen molecule (H 2 ). 如請求項2之方法，其中該出口流中之該水係來自在該水蒸汽產生器中結合依水分子化學計量之數量的氫分子(H2 )及氧分子(O2 )，且其中於該出口流中之該氫分子(H2 )係來自在該一或多個入口流中超過該依水分子化學計量之數量的氫分子(H2 )之一過剩數量之氫分子(H2 )。The method of claim 2, wherein the water system in the outlet stream is derived from a quantity of hydrogen molecules (H 2 ) and oxygen molecules (O 2 ) in a stoichiometric amount of water molecules in the water vapor generator, and wherein the hydrogen molecules of the outlet stream (H 2) by the number of lines exceeds the stoichiometric amount of hydrogen molecules of water molecules (H 2) and the excess amount of the hydrogen molecules (H 2) in the one or more inlet streams from . 如請求項3之方法，其中該氫對氧原子比為至多8：3。 The method of claim 3, wherein the hydrogen to oxygen atom ratio is at most 8:3. 如請求項1之方法，其中該結晶五氧化二鉭具有一(003)結晶取向。 The method of claim 1, wherein the crystalline antimony pentoxide has a (003) crystal orientation. 如請求項1之方法，其中該結晶五氧化二鉭係在沈積時(as-deposited)結晶。 The method of claim 1, wherein the crystalline antimony pentoxide is crystallized as-deposited. 如請求項1之方法，其中該方法不包括一退火步驟。 The method of claim 1, wherein the method does not include an annealing step. 一種形成一氧化物之方法，其包含：使一含釕材料與一包含一含鉭前驅物之蒸汽接觸；提供一包含一或多個入口流及一出口流之水蒸汽產生 器，其中該一或多個入口流包含氫分子(H2 )及氧分子(O2 )，且其中該一或多個入口流中之氫對氧比率係可控制的；及使該含釕材料與該出口流在於該含釕材料上形成結晶五氧化二鉭之條件下接觸。A method of forming an oxide comprising: contacting a ruthenium-containing material with a vapor comprising a ruthenium-containing precursor; providing a water vapor generator comprising one or more inlet streams and an outlet stream, wherein the Or a plurality of inlet streams comprising hydrogen molecules (H 2 ) and oxygen molecules (O 2 ), and wherein the hydrogen to oxygen ratio in the one or more inlet streams is controllable; and the cerium-containing material and the outlet stream are Contact is made under the condition that crystalline bismuth pentoxide is formed on the cerium-containing material. 如請求項8之方法，其中該出口流包含水及氫。 The method of claim 8, wherein the outlet stream comprises water and hydrogen. 如請求項8之方法，其中使用一氣相沈積製程實現使該含釕材料與包含一含鉭前驅物之該蒸汽接觸及使該含釕材料與該出口流接觸。 The method of claim 8 wherein the vapor-containing process is used to contact the vapor-containing material with the vapor comprising a ruthenium-containing precursor and to contact the ruthenium-containing material with the outlet stream. 如請求項10之方法，其中該氣相沈積製程為一包含複數個沈積循環之原子層沈積製程。 The method of claim 10, wherein the vapor deposition process is an atomic layer deposition process comprising a plurality of deposition cycles. 如請求項11之方法，其中該複數個沈積循環包含具有一第一氫對氧比率之至少一循環及具有一第二氫對氧比率之至少一循環，其中該第二氫對氧比率與該第一氫對氧比率不同。 The method of claim 11, wherein the plurality of deposition cycles comprise at least one cycle having a first hydrogen to oxygen ratio and at least one cycle having a second hydrogen to oxygen ratio, wherein the second hydrogen to oxygen ratio The first hydrogen to oxygen ratio is different. 如請求項12之方法，其中使用該第一氫對氧比率形成之該五氧化二鉭具有一與使用該第二氫對氧比率形成之該五氧化二鉭的結晶取向不同的結晶取向。 The method of claim 12, wherein the ruthenium pentoxide formed using the first hydrogen to oxygen ratio has a crystal orientation different from a crystal orientation of the ruthenium pentoxide formed using the second hydrogen to oxygen ratio. 如請求項8之方法，其中該含鉭前驅物具有式TaX5 ，其中每一X獨立地為一鹵基。The method of claim 8, wherein the ruthenium containing precursor has the formula TaX 5 wherein each X is independently a halo group. 如請求項14之方法，其中該含鉭前驅物為TaF5 。The method of claim 14, wherein the cerium-containing precursor is TaF 5 . 如請求項8之方法，其中有效之條件包含400℃至500℃的該含釕材料之一表面之一溫度。 The method of claim 8, wherein the effective condition comprises a temperature of one of the surfaces of the tantalum-containing material at 400 ° C to 500 ° C. 如請求項8之方法，其中該結晶五氧化二鉭具有至少50 埃之一厚度。 The method of claim 8, wherein the crystalline antimony pentoxide has at least 50 One thickness of angstrom. 如請求項8之方法，其中該氫對氧原子比為至少6：3。 The method of claim 8, wherein the hydrogen to oxygen atom ratio is at least 6:3. 如請求項8之方法，其中該氫對氧原子比為至多8：3。 The method of claim 8, wherein the hydrogen to oxygen atom ratio is at most 8:3. 一種形成一氧化物之方法，其包含：使一含釕材料與一包含一含鉭前驅物之第一蒸汽接觸；及使該含釕材料與一包含氫分子(H2 )及水之第二蒸汽在於該含釕材料上形成結晶五氧化二鉭之條件下接觸。A method of forming an oxide comprising: contacting a ruthenium-containing material with a first vapor comprising a ruthenium-containing precursor; and subjecting the ruthenium-containing material to a second comprising hydrogen molecules (H 2 ) and water The vapor is contacted under the conditions that the crystalline niobium oxide is formed on the niobium containing material. 一種物品，其包含：一第一電極，其包含一含釕材料；一在該第一電極之至少一部分上的第一結晶五氧化二鉭，其中該第一結晶五氧化二鉭具有一第一結晶取向；及一在該第一結晶五氧化二鉭之至少一部分上的第二結晶五氧化二鉭，其中該第二結晶五氧化二鉭具有一與該第一結晶取向不同之第二結晶取向。 An article comprising: a first electrode comprising a germanium-containing material; a first crystalline tantalum pentoxide on at least a portion of the first electrode, wherein the first crystalline tantalum pentoxide has a first a crystal orientation; and a second crystalline antimony pentoxide on at least a portion of the first crystalline antimony pentoxide, wherein the second crystalline antimony pentoxide has a second crystal orientation different from the first crystal orientation . 如請求項21之物品，其進一步包含一在該第二結晶五氧化二鉭之至少一部分上的第二電極。 The article of claim 21, further comprising a second electrode on at least a portion of the second crystalline antimony pentoxide. 如請求項21之物品，其中該第一結晶五氧化二鉭及該第二結晶五氧化二鉭中之至少一者具有一(003)結晶取向。 The article of claim 21, wherein at least one of the first crystalline antimony pentoxide and the second crystalline antimony pentoxide has a (003) crystal orientation. 如請求項21之物品，其中該第一結晶五氧化二鉭及第二結晶五氧化二鉭中之至少一者具有一(200)結晶取向。 The article of claim 21, wherein at least one of the first crystalline antimony pentoxide and the second crystalline antimony pentoxide has a (200) crystal orientation. 一種物品，其包含：一第一結晶五氧化二鉭；及一在該第一結晶五氧化二鉭之至少一部分上的第二結 晶五氧化二鉭，其中該第一五氧化二鉭具有一與該第二五氧化二鉭之結晶取向不同之結晶取向。 An article comprising: a first crystalline antimony pentoxide; and a second junction on at least a portion of the first crystalline antimony pentoxide The crystalline antimony pentoxide, wherein the first antimony pentoxide has a crystal orientation different from the crystal orientation of the second antimony pentoxide. 如請求項25之物品，其中該第一五氧化二鉭處於一基板上。 The article of claim 25, wherein the first tantalum pentoxide is on a substrate. 請求項25之物品，其中該第二五氧化二鉭直接處於該第一五氧化二鉭上。 The article of claim 25, wherein the second antimony pentoxide is directly on the first antimony pentoxide.
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